Phthalocyanine-Based Functional Polymeric Materials E-Book

Jianzhuang Jiang

• Herausgeber: Wiley-VCH
• Kategorie: Fachliteratur
• Sprache: Englisch

Seitenzahl: 605

Veröffentlichungsjahr: 2025

Beschreibung

A carefully curated collection of resources covering the concepts, perspectives, and applications of phthalocyanine chemistry

In Phthalocyanine-Based Functional Polymeric Materials: Design, Synthesis, and Applications, a team of distinguished researchers delivers a comprehensive discussion of phthalocyanine-involving hybrids, molecular cages, coordination polymers, covalent organic frameworks, and organic polymers. The book also explains a diverse array of the applications of these novel materials in chemical sensors, organic catalysts, electrocatalysis, photocatalysis, energy storage, and more.

The authors have included material designed to help you improve the design of monomers to synthesize polymers with desired functionalities. A valuable reference in the development of phthalocyanine chemistry, readers will also find:

• A thorough introduction to phthalocyanine-based polymers and their uses in sensors, catalysis, energy storage, and other applications
• Comprehensive explorations of the extended molecular systems of phthalocyanines, filling the gap between monomeric phthalocyanine compounds and polymers
• Practical discussions of a variety of phthalocyanine-based polymer systems, their potential applications, and major design and synthesis challenges
• Complete treatments of these novel materials appropriate for readers in academia and industry

Perfect for polymer, organic, inorganic, catalytic, complex, and structural chemists, Phthalocyanine-Based Functional Polymeric Materials will also benefit materials scientists and chemists working in industry.

Leseprobe

Table of Contents

Cover

Table of Contents

Title Page

Copyright

1 A Journey from Molecular Phthalocyanines to Polymeric Materials

1.1 Introduction

1.2 Monophthalocyanines

1.3 Phthalocyanine‐Based Oligomers

1.4 Phthalocyanine‐Based Polymeric Materials

1.5 Porous Polymeric Materials for Functional Applications

1.6 Conclusion

Abbreviations

References

2 Phthalocyanine‐Based Cages

2.1 Introduction

2.2 Phthalocyanine‐Based Cages

2.3 Electrochemical Properties of Pc‐Based Cages

2.4 Photophysical Properties of Pc‐Based Cage

2.5 Gas‐Sensing Properties of Pc‐Based Cage

2.6 Host–Guest Properties of Pc‐Based Molecular Cages

2.7 Conclusion

Abbreviations

References

3 Phthalocyanine‐Based Coordination Polymers

3.1 Introduction

3.2 Synthesis of Pc‐Based MOFs

3.3 Electrochemical Properties of Pc‐Based MOFs

3.4 The Nanocomposite of Pcs with Different MOFs Systems

3.5 The Axial Polymer of Pcs

3.6 The Polymers Based on the Co‐Assembly of Pcs with Cyclodextrin

3.7 The Nanocomposite of Pcs with MOFs and COFs

3.8 Conclusion

Abbreviations

References

4 Porous Phthalocyanine‐Based Organic Polymers

4.1 Introduction

4.2 Pc‐Based CMPs

4.3 Pc‐Based COFs

4.4 Polyphthalocyanines

4.5 Conclusion

Abbreviations

References

5 Sensors Based on Phthalocyanine Polymers and Covalent Organic Frameworks

5.1 Introduction

5.2 Basic Parameters for Sensors

5.3 Pc‐Based NO

2

/NH

3

/NO

2

−

Sensors

5.4 Pc‐Based

3

O

2

/

1

O

2

/H

2

O

2

Sensors

5.5 Pc‐Based Neurotransmitters and Stimulants Sensors

5.6 Pc‐Based Cancer Biomarker (L‐Cysteine) Sensors

5.7 Pc‐Based Glucose Sensors

5.8 Pc‐Based Ion Sensors

5.9 Pc‐Based Organic Compounds Sensors

5.10 Pc‐Based Temperature/Pressure Sensors

5.11 Conclusion

Abbreviations

References

6 Application of Phthalocyanine in Electrocatalysis

6.1 Introduction

6.2 Phthalocyanine for CO

2

Electroreduction

6.3 Phthalocyanine for ORR

6.4 Phthalocyanine for OER

6.5 Phthalocyanine for HER

6.6 Phthalocyanine for Nitrogen Reduction Reaction (NRR)

6.7 Phthalocyanine for Electrochemical H

2

O

2

Generation

6.8 Conclusion and Outlook

Abbreviations

References

7 Application of Phthalocyanine in Photocatalysis

7.1 Introduction

7.2 Phthalocyanine for CO

2

Photoreduction

7.3 Phthalocyanine for H

2

O

2

Photosynthesis

7.4 Phthalocyanine for Photocatalytic Degradation

7.5 Phthalocyanine for Photocatalytic Water Splitting

7.6 Conclusion and Outlook

Abbreviations

References

8 Applications of Phthalocyanine‐Based Polymeric Materials for Energy Storage

8.1 Introduction

8.2 Metal‐Ion Battery

8.3 Lithium‐Ion Battery

8.4 Sodium‐Ion Battery

8.5 Potassium‐Ion Battery

8.6 Metal–Air Battery

8.7 Li–O

2

Battery

8.8 Li–CO

2

Battery

8.9 Zinc–Air Battery

8.10 Supercapacitor

8.11 Aqueous Electrolyte System

8.12 Nonaqueous Electrolyte System

8.13 Gel Electrolyte System

8.14 Conclusions and Outlook

Abbreviations

References

Index

End User License Agreement

List of Tables

Chapter 5

Table 5.1 Performance of the polymer‐Pc H

2

O

2

electrode sensors.

Table 5.2 Performance of the polymer‐Pc dopamine electrode sensors.

Table 5.3 performance of the polymer‐Pc

L

‐CySH/

L

‐Met electrode sensors.

Table 5.4 Performance of the polymer‐Pc Glucose sensors.

List of Illustrations

Chapter 1

Figure 1.1 (a) Phthalocyanine core and various precursors (M = metal and 2H....

Figure 1.2 Preparation of metallic tetraaminophthalocyanine building block....

Figure 1.3 A Rosenmund‐von Braun reaction yields dicyanides, which are conve...

Figure 1.4 Structures of carboxyl‐bearing phthalocyanines.

Figure 1.5 Preparation of metallic octaaminophthalocyanine building block.

Figure 1.6 Schematic diagram of sandwich‐type phthalocyanine‐based complexes...

Figure 1.7 (a) Crystal structure of terbium(III)‐phthalocyaninato double‐dec...

Figure 1.8 General structures of homo‐ and heterometallic complexes in homo‐...

Figure 1.9 Zn(II) pyridino[3,4]tribenzoporphyrazine and two modes of self‐as...

Figure 1.10 Synthesis procedures of hexa‐

n

‐butoxyimidazolynylphthalocyaninat...

Figure 1.11 (a) Molecular structures of supramolecular triads MPc

2

–perilendi...

Figure 1.12 Synthesis of Pc–porphyrin‐fused dimers and trimers (M = 2H and Z...

Figure 1.13 Synthesis of tri‐

tert

‐butyliodophthalocyaninato zinc(II) and tri...

Figure 1.14 Synthesis of 1,8‐bis‐2′‐(9′,16′,23′‐trineopentyloxyphthalocyanin...

Figure 1.15 Cage‐promoted transformations of fullerenes.

Figure 1.16 The molecular and crystal structure of ZnPc′.

Figure 1.17 (a) Crystal structures of IRMOF‐n with general formula Zn

4

O[R(CO...

Figure 1.18 The synthesis procedure of the PCN‐135 with Zr

6

‐BTB layer and Pc...

Figure 1.19 Synthesis and STM (scanning tunneling microscopy) image of the 2...

Figure 1.20 The synthesis of NiPc‐COF by a boronate esterification reaction ...

Figure 1.21 (a) Stable 2D Pc COFs

Figure 1.22 PXRD data, structure, and properties of MPc‐O

8

‐Cu (a)

Figure 1.23 Synthesis of MPc‐CMPs (CMPs: conjugated microporous polymers) fo...

Figure 1.24 Schematic illustration of light‐driven CO

2

reduction property an...

Chapter 2

Figure 2.1 Cartoon representation of porous molecular cages.

Figure 2.2 Cartoon representation of metallacages and porous organic cages (...

Figure 2.3 Structures of porphyrin (Por) and phthalocyanine (Pc).

Figure 2.4 (a) The synthesis of Fe

2

Pc

3

metallo–organic helicate. (b) Side vi...

Figure 2.5 Schematic structure of ball‐type binuclear metal phthalocyanines ...

Figure 2.6 Schematic synthesis of ball‐type binuclear zinc phthalocyanine (P...

Figure 2.7 Reported precursors for fabricating ball‐type binuclear phthalocy...

Figure 2.8 The synthesis of ball‐type phthalocyanine (Pc) in two steps.

Figure 2.9 The synthesis of heterodinuclear ball‐type Pcs in two steps.

Figure 2.10 The synthesis of heterodinuclear ball‐type phthalocyanines (Pcs)...

Figure 2.11 The synthesis of hexanuclear phthalocyanine (Pc) by postmodifica...

Figure 2.12 The postmodification of ball‐type phthalocyanine (Pc), BT‐Pc‐7....

Figure 2.13 (a) The synthesis of the ZnPc and NiPc cages; (b) Side view and ...

Figure 2.14 Structure of subPc and subPc based cage.

Figure 2.15 Postulated photoredox mechanism for the conversion of C

60

.

Figure 2.16 (a) Self‐assembly of the fourfold rotaxane and (b) synthesis of ...

Figure 2.17 (a) Self‐assembly of the fourfold rotaxane and (b) the schematic...

Figure 2.18 (a) Fourfold rotaxane formation for the synthesis of [Cu(II)Pc‐H

Figure 2.19 Encapsulation of phthalocyanine (Pc) derivatives in octanuclear ...

Figure 2.20 Encapsulated Pcs according to the bent polyaromatic amphiphiles ...

Figure 2.21 (a) Concept and molecular design of a photoresponsive nanocapsul...

Figure 2.22 (a) Schematic synthesis of (peripherally and nonperipherally) su...

Figure 2.23 (a) The scheme of the primary Znair battery system with the Fe

2

P...

Figure 2.24 (a) Synthesis of a fourfold rotaxane heterodimer of porphyrin (P...

Figure 2.25 Schematic illustration of the preparation process for the M

2

Pc

2

(...

Figure 2.26 (a) The synthesis of the ZnPc and NiPc cages. (b) Partially bloc...

Figure 2.27 (a) Schematic synthesis of (peripherally and nonperipherally) su...

Figure 2.28 (a) Synthetic route for the linkage of ball‐type indium phthaloc...

Figure 2.29 (a) The structures of ball‐type homodinuclear Co(II)‐Co(II) phth...

Figure 2.30 (a) Schematic representation of the selective formation of host–...

Figure 2.31 (a) Minimum‐energy structures of (a) 1b, (b) 1b⊂C60, (c) 1b⊂C60:...

Chapter 3

Figure 3.1 The coordination polymers with phthalocyanines (Pcs) working as b...

Figure 3.2 Two‐step synthesis pathways for octahydroxy‐phthalocyanines (Pcs)...

Figure 3.3 The MOFs based on nickel phthalocyanine (Pc) can be active in the...

Figure 3.4 Conductive metal–organic frameworks (MOFs) based on phthalocyanin...

Figure 3.5 Bimetallic two‐dimensional (2D) metal–organic frameworks (MOFs) f...

Figure 3.6 Two‐dimensional (2D) conductive metal–organic frameworks (MOFs) w...

Figure 3.7 Metal–organic frameworks (MOF) PcCu‐O

8

‐Co were fabricated upon th...

Figure 3.8 (a) Structures of metal–organic framework (MOF) PcCu‐O

8

‐Zn; (b) T...

Figure 3.9 Fabrication of NiPc‐NiO

4

metal–organic framework (MOF) and the to...

Figure 3.10 Electroreduction of CO

2

to C

2

H

4

with high selectivity by using o...

Figure 3.11 Three‐dimensional (3D) Pc metal–organic frameworks (MOF) for ele...

Figure 3.12 Two‐step synthesis pathways for octaamino‐phthalocyanines (Pcs)....

Figure 3.13 Two‐dimensional (2D) nickel phthalocyanine (Pc) metal–organic fr...

Figure 3.14 Conductive Pc‐based metal–organic framework (MOF) can act as a h...

Figure 3.15 The surface‐modification of metal–organic framework (MOF) film f...

Figure 3.16 The synthesis of phthalocyanine (Pc)‐based metal–organic framewo...

Figure 3.17 Tuning electrochemical CO

2

reduction hierarchically by utilizing...

Figure 3.18 Synthesis of metallophthalocyanine (MPc)

CuPcSPy

and fabrication...

Figure 3.19 The synthesis of the zirconium‐based MOLs. Different L2 building...

Figure 3.20 The nanoparticle of coordination polymers containing phthalocyan...

Figure 3.21 The synergy of chem‐photodynamic therapy (PDT) and light/glutath...

Figure 3.22 Lieb‐lattice topological states of phthalocyanine (Pc) metal–org...

Figure 3.23 Two‐dimensional (2D) metal–organic framework (MOF)‐based on copp...

Figure 3.24 Two‐dimensional (2D)‐conjugated metal–organic frameworks (MOFs) ...

Figure 3.25 Fabrication and characterization of semiconducting K

3

Fe

2

[PcFe‐O

8

Figure 3.26 Phthalocyanine (Pc) two‐dimensional (2D)‐conjugated metal–organi...

Figure 3.27 Electrodeposition of two‐dimensional (2D) conductive metal–organ...

Figure 3.28 Conjugated PcCu‐metal–organic frameworks (MOFs)‐layered structur...

Figure 3.29 (a) De novo assembly upon metal–cation direction could encapsula...

Figure 3.30 The noncovalent encapsulation of phthalocyanine (Pc) within the ...

Figure 3.31 FA‐ZnPc@nano‐PFC‐16 with incorporated zinc phthalocyanine (ZnPc)...

Figure 3.32 The nanodrugs prepared upon incorporating phthalocyanines (Pcs) ...

Figure 3.33 Incorporation of zinc phthalocyanines (ZnPcs) into metal–organic...

Figure 3.34 The fabrication of E‐UiO‐66‐Pc through postsynthetic modificatio...

Figure 3.35 Fabrication of ZnTCPc/UIO‐66 composites.

Figure 3.36 Fabrication of CoTAPc–ZIF‐90 composites containing phthalocyanin...

Figure 3.37 Phthalocyanine (Pc)/metal–organic frameworks (MOFs) nanocomposit...

Figure 3.38 The nanocomposites containing iron(II) phthalocyanine (Pc) and z...

Figure 3.39 Fabrication of Pd@CuPc/metal–organic framework (MOF) composite v...

Figure 3.40 The fabrication of iron phthalocyanine (FePc)@Ni‐metal–organic f...

Figure 3.41 Cr‐metal–organic framework (MOF) co‐assembled with cobalt phthal...

Figure 3.42 CuPc@IRMOF‐3 core–shell heterostructures exhibit remarkable sens...

Figure 3.43 The metal(II) phthalocyanine (Pc) coordination polymers with opt...

Figure 3.44 (a) Nanoporous crystalline metal–organic framework (MOF) in the ...

Figure 3.45 (a) The quasi‐metal–organic framework (MOF) nanowires can be fab...

Figure 3.46 The pyrolysis of γ‐cyclodextrin MOFs (γCD‐MOF) encapsulating iro...

Figure 3.47 The integrated electrochemiluminescence probe containing TiO

2

MO...

Figure 3.48 (a) Fabrication of Cu‐MOF@CuPc‐TA‐COF hybrid composites and (b) ...

Figure 3.49 Assembly of metal–organic framework (MOFs) with covalent organic...

Chapter 4

Figure 4.1 The classification of Pc‐based POPs.

Figure 4.2 Synthesis of triptycene‐based CMP (Trip‐Pc‐PIM).

Figure 4.3 The preparation of MPc‐CMPs based on MPc(NH

2

)

4

various multi alde...

Figure 4.4 (a) Schematic construction of iminium‐linked CONs. (b–e) FT‐IR, N...

Figure 4.5 Schematic synthesis of the ethynyl‐linked Pc‐based CMPs.

Figure 4.6 (a) Schematic preparation of CMP(CoPc‐H

2

Pc) and (b) CNT@CMP(CoPc‐...

Figure 4.7 The used Pc monomers (a) and linkages (b) for construction of COF...

Figure 4.8 The schematic synthesis and structure of the nickel Pc COF NiPc‐P...

Figure 4.9 Reticular frameworks of ZnPc COFs composed of zinc Pcs unit and p...

Figure 4.10 Schematic preparation (a),

13

C ssNMR spectrum (b), PXRD pattern ...

Figure 4.11 PXRD data, structures, SEM, TEM, HRTEM, and EDS mapping photos o...

Figure 4.12 Schematic synthesis of phenazine‐linked CoPc‐PDQ‐COF by polymeri...

Figure 4.13 Preparation route of crystalline NiPc‐CoTAA framework.

Figure 4.14 Synthetic route of the imidazole‐linked BICuPc‐COF‐1, BICuPc‐COF...

Figure 4.15 Schematic synthesis of NiPc‐Salen(Co)

2

‐COF and NiPc‐Salen‐COF.

Figure 4.16 Synthesis of MPc‐Pi‐COF‐1, MPc‐Pi‐COF‐2, and MPc‐Pi‐COF‐3.

Figure 4.17 Schematic structures of MPc‐DAPor and MPc‐TAPor (M = Co and H

2

) ...

Figure 4.18 Synthesis, crystal structures, PXRD data as well as SEM and HRTE...

Figure 4.19 Synthesis of dioxin‐linked COFs, including CuPcF

8

‐CoPc‐COF and C...

Figure 4.20 Schematic diagram for the synthesis of M

1

Pc‐NH‐M

2

PcF

8

COFs (M

1

 ≠...

Figure 4.21 The structure of homo/heterometallic polyphthalocyanine (MPPc)....

Figure 4.22 Synthetic synthesis of FeMoPPc catalyst.

Figure 4.23 Catalyst synthesis and morphology characterization Fe‐PPc‐F.

Figure 4.24 Synthesis and morphology characterization of Fe‐PPc@X‐CNTs.

Figure 4.25 Schematic synthesis procedure and various characterizations of P...

Figure 4.26 Schematic illustration of synthesis for edged‐functionalized CoP...

Figure 4.27 Schematic preparation of PzFeTPr and various characterizations....

Chapter 5

Figure 5.1 The Langmuir isotherm for nondissociative adsorption for differen...

Figure 5.2 Synthesis route to PorCoPc‐CMP and the response/recovery curves o...

Figure 5.3 The fabrication process of the NiPc(OH)

4

/PEO‐GCE.

Figure 5.4 The synthesizing route of PVA‐PdTPPS, and its phosphorescence, de...

Figure 5.5 (a) Schematic diagram depicting the chemical structures of (upper...

Figure 5.6 (a) Schematics for the amperometric sensing of H

2

O

2

using CoTBIPc...

Figure 5.7 Synthetic route for preparing CoTABAPc and mechanism of oxidative...

Figure 5.8 Reaction mechanism of nicotine oxidation in polyNiTSPc.

Figure 5.9 The density functional theory (DFT) modeling focuses on the inter...

Figure 5.10 Schematic description of the catalytic reaction at the bilayer e...

Figure 5.11 The synthesizing route of CuMAPc, which is covalently attached t...

Figure 5.12 (Upper) Synthesis of copper phthalocyanine (CuPc), 2,9,16,23‐tet...

Figure 5.13 (Left) Synthesizing route of MnClPc(MOR‐NAF), TiOPc(MOR‐NAF), an...

Figure 5.14 Constructing mechanism from CEC to EPS, the interaction between ...

Figure 5.15 (a) Construction of EPS with CEC, the interaction of the pestici...

Figure 5.16 Schematic illustration of synthetic MPorPc‐CMP and a possible ph...

Figure 5.17 (a) Synthesizing route of cobalt phthalocyanine (CoPc) sheet pol...

Figure 5.18 Simulating experiments, image recognition algorithm, and EWC res...

Figure 5.19 High‐resolution temperature sensor fabricated with composed PEDO...

Chapter 6

Figure 6.1 (a) Schematic presentation for the fabrication of CuPcF

8

‐CoPc‐COF...

Figure 6.2 (a) Schematic presentation of the synthesis of PyNiPc/CNT. (b) TE...

Figure 6.3 (a) Crystal configuration of an asymmetric NiPc(OH)

6

(DCNFO) molec...

Figure 6.4 (a) Structure illustration of PcCu‐TFPN. (b) FEs of CO

2

RR yields ...

Figure 6.5 (a,b) Synthesis of MPc‐PI‐COF‐3 (M = Co

II

, H

2

). (c) FE diagrams o...

Figure 6.6 (a) Schematic synthesis of NiPc‐CoPor‐imi‐COF. (b) FE

CO

. (c) Stab...

Figure 6.7 (a) Structures of Type 1 : 2 (CoPc‐2H

2

Por, H

2

Pc‐2H

2

Por) and Type ...

Figure 6.8 (a) Schematic preparation process of CoPc‐DNDS‐COF and CoPc‐DSDS‐...

Figure 6.9 (a) Schematic illustration of the synthesis and structure of CuPP...

Figure 6.10 (a) Schematic preparation illustration of CoPc©Fe‐N‐C. (b) High‐...

Figure 6.11 (a) Illustration of the synthesis of NiPc‐NiO

4

. (b) HAADF‐STEM i...

Figure 6.12 (a) Schematic illustration of the mixed‐metal salt method for th...

Figure 6.13 (a) Schematic illustration of the fabrication of NiPc‐Salen(Co)

2

Figure 6.14 (a) Schematic illustration for the fabrication of

p

MPcs (M = Fe,...

Figure 6.15 (a) Schematic illustration for the fabrication of isoreticular M...

Figure 6.16 (a) Structures of building units (M = 2H and Metal): 2,3,9,10,16...

Figure 6.17 (a) Synthesis of NiPc‐H‐COF, NiPc‐OH‐COF, and NiPc‐OMe‐COF. PXRD...

Figure 6.18 (a) Scheme of Pz‐FeTPr (left: top view; right: side view). (b) H...

Figure 6.19 (a) Schematic structure of PcCu‐O

8

‐M (red: O, blue: carbon, whit...

Figure 6.20 (a) Preparation route of CoFe‐COP/OMC. (b) HAADF‐STEM image for ...

Figure 6.21 (a) Schematic diagram of the preparation for the 2D MCOF contain...

Figure 6.22 (a) Schematic synthetic process of MPc‐pz (M = Fe, Co, Ni, Cu, a...

Figure 6.23 (a) Schematic presentation of CuTAPc‐BPy‐COF and CuTAPc‐CuBPy‐CO...

Chapter 7

Figure 7.1 (a) Schematic illustration of light‐driven CO

2

reduction catalyze...

Figure 7.2 (a) Schematic illustration of CoPcPDA‐CMP NSs synthesis. (b) Phot...

Figure 7.3 TEM (a) and HRTEM (b) images of P‐WO

3

, and TEM (c) and HRTEM imag...

Figure 7.4 (a) Molecular structures of the catalysts (CoFPc ans CoPc), a pho...

Figure 7.5 (a) Synthesis of g‐C

3

N

4

/CoPc‐COOH photocatalyst. (b) Methanol yie...

Figure 7.6 (a) View of the cage matrix in the crystal structure of Pc‐Co@1. ...

Figure 7.7 (a) Schematic diagram of the synthesis of the NiTAPc‐BPMDA COF. (...

Figure 7.8 (a) Schematic illustration of NCB‐3

Z

‐scheme heterojunction. (b) ...

Figure 7.9 The optimized configurations of NiPC‐TFPN‐CoFs (a), CoPC‐TFPN‐CoF...

Figure 7.10 Schematic of the formation of ultrathin CoPc/P‐BNDCN heterostruc...

Figure 7.11 (a) Schematic synthesis of CoPc‐BTM‐COF and CoPc‐DAB‐COF. (b) PX...

Figure 7.12 (a) Synthesis of MPc‐THHI‐COF (M = 2H and Ni). (b) Simulated pac...

Figure 7.13 (a) Schematic diagram of the preparation of CuPc‐PACA HIOBs. (b)...

Figure 7.14 (a) Synthetic illustration of the NiPc–FePc/BCN heterojunction p...

Figure 7.15 (a) Schematic illustration of incorporation of ZnPc (green) into...

Figure 7.16 (a) Synthetic illustration of the ultrathin CoPc/P‐CN nanocompos...

Figure 7.17 (a) Schematic for the synthesis process of g‐C

3

N

4

/ZnTcPc/GQDs. (...

Figure 7.18 (a) Schematic of preparing H

2

‐treated FePc/(100)Bi

2

MoO

6

ultrathi...

Figure 7.19 Synthesis routes of (a) α‐ZnPc‐CMP and (b) β‐ZnPc‐CMP. (c) Compa...

Figure 7.20 (a) The schematic illustration for the synthesis process of MPc‐...

Figure 7.21 (a) The preparation and exfoliation process of iron phthalocyani...

Figure 7.22 (a) Structures of zinc phthalocyanine derivative (Zn‐tri‐PcNc) a...

Chapter 8

Figure 8.1 Schematic structure of metal ion battery.

Figure 8.2 (a) Synthesis and structure scheme of Cu‐CuPc. (b) Discharge and ...

Figure 8.3 (a) Synthesis of TTF‐SiPc and its μ‐oxo oligomers. (b) Schematic ...

Figure 8.4 (a) Schematic structure of BDC‐NiPc. (b) Charge/discharge and (c)...

Figure 8.5 (a) Schematic structure of PMDA‐NiPc‐G. (b) Cyclability of the gr...

Figure 8.6 (a) Energy‐level diagrams of CuTAPc and its dimer obtained from D...

Figure 8.7 (a) Synthesis of CuPcNA‐CMP. (b) The structure evolution and the ...

Figure 8.8 (a) Schematic representation of the deposition of lithium on the ...

Figure 8.9 (a) Schematic illustration of preparing the S@TCP/MCs electrode. ...

Figure 8.10 (a) Schematic structure, (b) cycling performance, and (c) electr...

Figure 8.11 (a) Schematic illustration of the polymeric disodium phthalocyan...

Figure 8.12 (a) Top and side views of the sodium‐inserted CuPc‐2D‐cCOF. (b) ...

Figure 8.13 (a) Schematic modeling and chemical structures of conjugated PcC...

Figure 8.14 (a) Ionothermal synthesis approach toward the construction of BB...

Figure 8.15 Schematic diagrams and principles of operation of (a) nonaqueous...

Figure 8.16 (a) Schematic diagrams of the structure of CoPc, CoPPc, and D‐Co...

Figure 8.17 (a) Schematic of the CuPPc‐CNTs‐based Li‐CO

2

battery. (b) Cycle ...

Figure 8.18 (a) Synthesis and structural schematics and (b) AFM of CoPc‐Mn‐O...

Figure 8.19 (a) Schematic structure of PcCu‐O

8

‐M. (b) ORR polarization curve...

Figure 8.20 (a) Schematic synthesis of the 

pf

SAC‐Fe catalyst. (b) LSV curves...

Figure 8.21 (a) Synthetic scheme of the CAN‐Pc(M) catalysts for efficient OR...

Figure 8.22 (a) Schematic structure of CAN‐Pc(Co)‐

x

. (b) Pattern of CAN‐Pc(C...

Figure 8.23 (a) Schematic of the synthesis of MPc‐CPs. (b) LSV curves of Fe

0

...

Figure 8.24 (a) Schematic of the synthesis for FePc‐BBL COF. (b) LSV curves ...

Figure 8.25 (a) Schematic illustration of the synthesis of NiO

x

@FePc‐PI/KB. ...

Figure 8.26 (a) Structural diagram of COP

BTC

‐M. (b) ORR and OER activity of ...

Figure 8.27 (a) ∼ (d) Comparison of the electrochemical behavior for a typic...

Figure 8.28 (a) Synthesis of Pc‐CPN‐2 from HAT(CN)6. (b) BET surface areas o...

Figure 8.29 (a) Schematic synthesis of the Ni

2

[CuPcS

8

]. (b) Galvanostatic ch...

Figure 8.30 [(a) and (b)] Illustration of a symmetric supercapacitors (SSCs)...

Guide

Cover

Table of Contents

Title Page

Copyright

Begin Reading

Index

End User License Agreement

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Phthalocyanine‐Based Functional Polymeric Materials

Design, Synthesis, and Applications

Jianzhuang Jiang, Hailong Wang, and Kang Wang

Authors

Prof. Jianzhuang JiangUniversity of Science and TechnologyBeijingXueyuan Road 30Beijing 100083China

Prof. Hailong WangUniversity of Science and TechnologyBeijingXueyuan Road 30Beijing 100083China

Prof. Kang WangUniversity of Science and TechnologyBeijingXueyuan Road 30Beijing 100083China

Cover Image: © Jianzhuang Jiang

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Print ISBN: 978‐3‐527‐35122‐0ePDF ISBN: 978‐3‐527‐84008‐3ePub ISBN: 978‐3‐527‐84009‐0oBook ISBN: 978‐3‐527‐84010‐6

1A Journey from Molecular Phthalocyanines to Polymeric Materials

1.1 Introduction

Throughout the progress of human civilization, innovations in materials always promote the breakthrough of science and technology, resulting in the great promotion of productivity and the tremendous development of human society. In other words, materials are the foundation of civilization development. A variety of materials covering stone, copper, bronze, iron, inorganic silicon, and organic molecular and polymeric species successively innovate tools, methods, and even ideology that have not only survived human beings from nature's challenges but also endowed them the comprehensive capability to resist and use nature [1]. Thus far, new materials design and preparation still highly contribute to the technological innovations for targeted applications. This could guarantee plenty of energy resources' supply, health and longevity of humankind, and sustainability of economy, ecology, and civilization [1]. In this regard, chemistry has always aimed to produce new matters and to understand the structures and functions behind these matters for predicting desired functions [2]. In classical chemistry, chemists intend to prepare pure inorganic and molecular compounds by means of the broken and formation of strong covalent bonds into/from atoms for understanding nature from atom and molecular perspectives [2]. These well‐defined materials are different from those of the most important biological systems with imprecise structures assembled from non‐covalent interactions. It is worth noting that the dynamic nature of biological architectures originated from weak interactions, which plays an important role in the complicated physiological activity of living systems. In this context, the enormous difference in structures together with properties and functions between the artificial and natural chemical compounds arouse the renovations of materials synthesis approaches through the mode of atom by atom and/or molecule by molecule.

Supramolecular chemistry is also well known as “chemistry beyond the molecule.” [2] It has been established since 1987 as a result of the Nobel Prize in Chemistry awarded to Donald J. Cram, Jean‐Marie Lehn, and Charles J. Pedersen “for their development and use of molecules with structure‐specific interactions of high selectivity.” [2] Since then, supramolecular chemistry has flourished following its application in the organization of chemical systems to mimic biological processes, bridging biological and materials science. However, the initial study in the field of supramolecular chemistry focused on molecular recognition phenomena as early as and even before macrocyclic chemistry, crown ether chemistry, and host–guest chemistry has emerged to enrich the concepts and perspectives in the field of supramolecular chemistry [3]. In the recent 20 years, the intrinsically dynamic characteristic of supramolecular chemistry has gradually attracted attention, expanding its scope to the dynamic covalent chemistry and dissipative self‐assembly processes [4]. In the future, there must be still many directions that will be discovered from comprehensive researches.

Today, the development of materials design and preparation still continues to focus on their eternal theme applications for enabling sustainable global resources and environments as well as human health [5]. Simultaneously, there are many efforts dedicated to molecular engineering by using atoms and molecules to assemble polymeric materials toward the targeted properties and functions, providing a bottom‐up approach to prepare polymeric structures through various interactions. Molecular engineering of the interactions and spatial arrangement of rationally selected molecular modules holds promise for fine‐tuning the functions of molecule‐based materials. Instead of the sole discussion of strong chemical interactions between atoms in molecules, the advancement of polymeric materials requires understanding the relationships between the functions and the complicated factors that are involved in the polymeric structural materials beyond molecular components. From atomic and molecular perspectives, the well‐defined polymeric assemblies in crystalline states are very helpful in precisely correlating the structure‐function relationships behind the increased complexity of these materials architecture because their well‐defined chemical structures enable the elucidation of their electronic structures. In this direction, metal–organic frameworks (MOFs, since 1999) [6], covalent organic frameworks (COFs, 2005) [7], metal‐organic cages (MOCs, 1995) [8], and various porous organic crystals including porous organic cages (POCs, 2009) [9] and hydrogen‐bonded organic frameworks (HOFs, 1994) [10] have been established, which enrich the “chemistry of the framework.” Their constituent components with variable geometries, sizes, and functions play an important role in attaining designable structural topology, adjustable homogeneous porosity, and tunable functionalities for these materials, enabling a lot of diverse applications in the field of gas storage, separation, catalysis, and energy storage and conversion. In particular, the open frameworks usually have permanent nanometer‐sized voids that ensure molecular recognition, chemical storage, stereoselective conversion of molecules, and powerful support to encapsulate various nanomaterials of metals, metal oxides, semiconductors, and complexes. As a result, these frameworks have always attracted the wide and intense attention of researchers from chemistry and materials fields.

Phthalocyanines (Pcs) are very important blue or green commercial pigments used in inks, as a dyestuff for textiles, and as a colorant for metals and plastics due to the intense Q‐bands at 620–700 nm, and their history is dated from 1928 [11–13]. The characterizations of their structures were first introduced in 1934 [14–17]. X‐ray diffraction analyses performed by Robertson clearly reveal that the planar macrocyclic molecular structure of Pc contains the four isoindole units connected by four aza‐bridges [18–20], possessing an 18‐electron aromatic cloud delocalized over 16 alternated carbon and nitrogen atoms surrounding the N4 cavity. Such a macrocyclic structure for artificial Pcs is very similar to that of the naturally occurring porphyrins (Pors), exhibiting strong electronic absorption ability in the visible light region and an excellent photosensitive property to fast transfer energy and/or electron to its acceptor counterparts [21–23]. Therefore, Pcs are also widely investigated in artificial photosynthetic systems and nanomedicines due to their huge molar absorption coefficients in the red near‐infrared range, fluorescence, phosphorescence, singlet oxygen generation quantum yields, and adjustable photochemical properties from molecular perspective [22–27]. For example, Pcs have been used as important photosensitizers for fluorescence imaging and photodynamic therapy [26, 27]. Different from Pors, Pcs also have significant thermal and chemical stability due to the special conjugation structures, supporting the harsh sublimation process and intense electromagnetic radiations. As a result, the well‐defined structure of metal‐free Pc (H2Pc) as the first organic compound was resolved using single‐crystal X‐ray diffraction (SCXRD) technology [28].

The remarkable versatility of molecular Pcs could be further improved by replacing the central two hydrogen atoms in the N4 cavity with more than 70 metals as well as by introducing the functional substituents on the non‐peripheral (α) and peripheral (β) positions and even the axial positions of the macrocycle (Figure 1.1). In particular, the large homo‐ and heterometallic ions (e.g. rare earths [REs], actinides, and group 4 transition metals) enable the complexation with macrocycles to form sandwich‐type complexes in the form of double‐, triple‐, quadruple‐, quintuple‐, and sextuple‐decker structures. The intramolecular π‐π interactions and the metal attributes make these compounds interesting properties and good device candidates in the field of field‐effect transistors, molecular magnets, information storage materials, and sensors. The intrinsic monomolecular and supramolecular characteristics of Pcs therefore are not only fine‐tuned but also greatly innovated due to the macrocycle metalation and modification. Thus far, Pcs have been well developed and widely explored in the field of fundamental research and industrial and technological areas. They have been used as active components to fabricate semiconductors [29], chemo‐sensors [30, 31], electrochromic displays [32, 33], information storage devices [34, 35], liquid crystals [36, 37], photovoltaic cells [38, 39], catalysts [40, 41], and nonlinear optics and optical limiting materials [42–44]. In addition to possessing diverse chemistry, molecular Pcs serve as functional building blocks (also named synthons) to assemble multicomponent and even polymeric systems [40–42, 45]. The diversity of linkages and modules provides the abundant assembly chemistry of Pcs macrocycles, further broadening their applicability and strengthening their stability toward practical use. It is worth noting that the spatial arrangement of Pcs macrocycles, module types, and connection modes is crucial for the positive expression of their functionalities and properties. The supramolecular and covalent organization guarantees the fine control of the spatial arrangement of Pcs building blocks and/or appropriately paired counterparts. The corresponding structure and property studies are of importance and compatible with each other from supramolecular and covalent polymer levels. Within this context, the porosity formed by the stacking Pcs macrocycles is able to take advantage of the substrate confinement, diffusion, and activation, enabling the formation of a kind of unique porous polymeric material.

Figure 1.1 (a) Phthalocyanine core and various precursors (M = metal and 2H. 1, 4, 8, 11, 15, 18, 22, 25 and 2, 3, 9, 10, 16, 17, 23, 24 sites are non‐peripheral (α) and peripheral (β) positions, respectively. The substituents are omitted for clarity). (b) Partial phthalocyanine precursors.

In this chapter, we intend to summarize the preparation and applications of functional Pcs to provide a basic research background for the focused polymeric materials research in this book. Their basic synthetic methods ensure the preparation of powerful monomers for constructing polymeric materials through various reactions occurring on the active moieties. We also describe how the versatile chemistry makes the Pc materials evolve from monomers, oligomers, composites, supramolecular assemblies, dendrimers, to polymers. In addition, we focus on the most recent contributions in functional Pcs mainly since 2010, and the outstanding paradigms of Pc‐based polymeric materials (MOFs and COFs) and applications (electrocatalysts, sensors, etc.) are also introduced. These diverse heterogeneous application studies at the molecular level accumulate enough knowledge to improve the functionalities of polymeric materials.

1.2 Monophthalocyanines

Molecular engineering is the main ideological system passing through the design and preparation of materials made up of discrete molecules for the targeted function, requiring precise understanding and thus tuning the structure–function relationships inherited in the molecule‐based materials at the atomic/molecular level. A large number of factors that are involved in the assembly of molecular (microscopic) components to aggregated (macroscopic) solids increase the complexity in correlating the structure–function relationships of the latter complicated materials than those of their individual building blocks. These factors across a number of length scales, including the changed microscopic environments of molecular modules in materials, the connection modes, spatial arrangement, aggregated degrees, materials defects, sizes and morphologies of materials, and working environments, etc. These principles in molecular engineering are certainly suitable for the development of Pc‐based polymeric materials. To date, Pcs have been demonstrated as versatile molecular modules in the assembly of polymeric materials through appropriate organization modes and linkages [46–48]. Many efforts in engineering the properties of these materials depend on bottom‐up approaches based on molecular Pcs for fabricating composite polymeric structures toward rational optimization of their practical and multifaceted functions [49–53]. Within this context, the design and preparation of molecular Pcs is of prime importance, ensuring the successful assembly of these macrocyclic building blocks into the desired spatial arrangements for obtaining optimal optoelectronic properties.

Phthalonitriles, phthalic anhydride, phthalimide, and 1,3‐diiminoisoindoles are common starting materials for the preparation of molecular Pcs for constructing supramolecular and covalent‐bonded composites and polymeric compounds (Figure 1.1). The cyclization arrangement of aza‐connected four isoindole units at their 1,3‐positions in a reasonable yield usually occurs with the help of metal ion template (such as metal, salt, alkoxide, or metal salt/organic amine) reaction under a solution upon reflux in C3–C8 alcohols at 100–200 °C or in 2‐(N,N‐dimethylamino [DMF]) ethanol at 135 °C [54]. For solution reactions, the non‐nucleophilic base catalysts such as 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) are necessarily employed for the formation of Pcs. For example, the preparation of metallic macrocycles (NiPcs) has been demonstrated from phthalonitrile with the help of divalent nickel salt in a solution of amine (e.g. quinoline, DMF, ethanol, DBU, and urea), hydroquinone, and alkali and additional activation by microwave or ultraviolet (UV) irradiation [55]. In good contrast, solid‐state reactions have emerged as a sustainable and environmentally friendly approach to obtain Pc chemicals due to the avoidance of solvent use. These synthetic routes have been previously summarized in several reviews and books, detailing various smart methods of symmetric and asymmetric Pc molecules [12]. In recent years, mechanochemical preparation has been studied to couple with solid‐state synthesis of Pcs for further promoting the production yield and the direct synthesis of composite materials for diverse applications [56]. In this section, the contributions in the design and synthesis of Pc compounds with active sites for aggregation and polymerization, which could be extended from molecules, oligomers to diverse composites and assemblies, have been selectively introduced for the after‐mentioned research. Actually, the chemical alternations on the four benzene rings at the α and β positions of Pcs are basically achieved using various organic synthetic methods (Figure 1.1). The incorporation of active groups mainly occurs on β positions of Pc scaffolds. Four or eight functional groups including amino groups, carboxylic groups, hydroxyl groups, cyano groups, iodine atoms, fluorine atoms, and alkynyl groups on macrocyclic rings are helpful in the polymerization of discrete molecular modules into various photoactive and/or electroactive coordinate‐ and covalent‐bonded assemblies as well as multicomponent systems. In the following section, we present the preparation of four‐ and eight‐substituted Pcs to introduce these building blocks with four and eight active atoms/groups, respectively.

1.2.1 Tetra‐Substituted Monophthalocyanines

Among the above‐mentioned active groups, the nature of amino, carboxyl, hydroxyl, and cyano species of Pcs permits both coordination and covalent polymerization. In contrast, iodine atoms, fluorine atoms, and alkynyl groups allow only covalent expansion of Pc macrocycles. Pc macrocycles attached by four amino groups attract great interest due to the simple preparation process of their nitro‐substituted macrocycle precursor. All 4‐nitrophthalonitrile, 4‐nitrophthalic anhydride, 4‐nitrophthaloimide, and 4‐nitrophthalic acids as starting materials have been converted into macrocyclic Pcs present in various metal salts according to the reported literature [57–59]. For example, the reaction of metal salts, 4‐nitrophthalic acid, ammonium chloride, ammonium molybdate, and urea in nitrobenzene at 185 °C led to the generation of metallic tetranitrophthalocyanine isomers, which was further reduced by Na2S to obtain the corresponding tetraaminophthalocyanine with yield up to 90%. Such preparation method was suggested to obtain metallic tetraaminophthalocyanine‐containing metals with ionic radii of about 0.8 Å, including copper, cobalt, nickel, zinc, iron, platinum, aluminum, and vanadium (Figure 1.2).

In addition, the preparation of Pcs with active iodine substituents is also of high interest because the functional group allows the chemical modification to provide new building blocks for polymeric structures through metal‐catalyzed reactions. The high diversity of the functionalization via arylhalides precursors has been demonstrated as indicated by various organic synthetic materials. Herein, zinc tetraiodophthalocyanine is taken as a representative, which is prepared using a solid reaction of 4‐iodo‐phthalonitriles with metal salt at 220–250 °C [60]. Then, vinylsulfo groups were attached to on the isoindole rings of zinc tetraiodophthalocyanine through its Heck reaction with sodium vinylsulfonate with the help of Pd(II)acetate catalyst. Such a strategy allows the fabrication of not only acetylene‐ or vinyl‐containing Pcs but also a wide range of functional group‐attached scaffolds. In contrast to the chemical synthesis from tetraiodophthalocyanine as precursors, there is an example for the direct synthesis of functional Pc building blocks using functional dicyanide. The terpyridine precursor (4′‐(4,5‐dibromo‐2‐methylphenyl)‐2,2′:6′,2″‐teryridine) was provided based on the Kröhnke method using 4,5‐dibromo‐2‐methylbenzaldehyde to react with 2‐acetylpyridine and then 1‐(2‐pyridylcarbonylmethyl)pyridinium iodide with the assistance of ammonium acetate [61]. In the following step, a Rosenmund‐von Braun reaction of 4′‐(4,5‐dibromo‐2‐methylphenyl)‐2,2′:6′,2″‐teryridine with CuCN gave the dicyanide compound (4′‐(4,5‐dicyano‐2‐methylphenyl)‐2,2′:6′,2″‐teryridine), which proceeded the cyclization to provide the corresponding zinc Pc bearing four terpyridine units by refluxing in 2‐(dimethylamino)ethanol containing ZnCl2 (Figure 1.3). The terpyridyl‐containing Pc and another mono‐terpyridine ligand were used to assemble multicomponent systems composed of Pcs and bis(terpyridyl) metal complexes through a stepwise synthetic procedure.

Figure 1.2 Preparation of metallic tetraaminophthalocyanine building block.

Figure 1.3 A Rosenmund‐von Braun reaction yields dicyanides, which are converted into the corresponding ZnPc by refluxing in 2‐(dimethylamino)ethanol in the presence of ZnCl2.

Carboxyl and sulfo groups are active sites for supramolecular and covalent composites and polymers. The preparation of carboxyl‐attached Pcs is taken as an example. For the Pcs with carboxyl groups attached to on the peripheral positions, they are prepared by the reaction of trimellitic anhydride, urea, and metal salts in nitrobenzene with the help of a catalyst followed by the hydrolysis reaction [62]. In addition, the substitution of 4‐nitrophthalonitrile, 4,5‐dichlorophthalonitrile, or 3,4,5,6‐tetrachlorophthalonithrile with ethyl 4‐hydroxy‐3‐methoxybenzoate generates the corresponding phthalonitrile derivatives (Figure 1.4). The carboxyl‐containing Pcs have been prepared by the above‐mentioned conventional methods. The functional substituents in the isoindole ring of Pcs could enhance their solubility due to the steric strain inhibiting the π‐π interaction of the macrocycle [63, 64].

1.2.2 Octa‐Substituted Monophthalocyanines

Octa‐substituted Pc building blocks are those molecules with eight substituents including amino, carboxyl, hydroxyl, fluorine, and cyano species located on the peripheral positions of the macrocycle. Generally, these monomeric Pcs are prepared from their corresponding phthalonitriles followed by the necessary deprotection and metalation. For 2,3,9,10,16,17,23,24‐octaaminophthalocyanine, its starting material, o‐phenylenediamine, was first tosylated with tosyl chloride, brominated by liquid Br2, and then reacted with CuCN to generate 4,5‐dicyano‐N,N′‐ditosyl‐o‐phenylenediamine. Metal‐free 2,3,9,10,16,17,23,24‐octaaminophthalocyanine was achieved through protonation of the dilithium Pc intermediate prepared by heating n‐pentanol containing lithium and dicyanide compounds followed by a proton–lithium exchange. In contrast, the cyclotetramerization reaction of 4,5‐dicyano‐N,N′‐ditosyl‐o‐phenylenediamine in the presence of the metal salt and DBU in refluxing n‐hexanol led to metallic species [65]. 2,3,9,10,16,17,23,24‐Octaamino‐phthalocyanine nickel(II) was prepared by the deprotection in the presence of H2SO4 (Figure 1.5) [66]. Obviously, most phthalonitriles as Pcs' precursors are prepared by the energy‐ and time‐consuming synthesis process, including the introduction of a protective group, bromination, and cyanidation. The necessary deprotection is required for those Pc molecules with active sites for the next assembly. As a result, the improvement of the synthesis route for symmetric Pcs is of significance for the development of polymeric materials. It is worth noting that the axial ligand coordination of Pcs provides another possible approach to construct polymeric materials. In this direction, silicon or ruthenium Pcs are also modules for the introduction of axial ligands to assemble oligomers and dendrimers. In addition, some molecular Pcs with four different isoindole rings (denoted as asymmetric species) are also useful building blocks for the construction of oligomers and polymers, which are prepared by mixed phthalonitriles, usually exhibiting a low yield after tedious separation.

Figure 1.4 Structures of carboxyl‐bearing phthalocyanines.

Figure 1.5 Preparation of metallic octaaminophthalocyanine building block.

1.3 Phthalocyanine‐Based Oligomers

1.3.1 Sandwich‐Type Phthalocyanine‐Based Complexes

Sandwich‐type tetrapyrrole compounds are classified as homoleptic and heteroleptic species. Homoleptic sandwich‐type compounds are made up of the same phthalocyaninato or porphyrinato ligands (Figure 1.6). In contrast, heteroleptic compounds constitute two different tetrapyrrole ligands, which belong to the same subclass of species. When the sandwich‐type compounds involve two kinds of tetrapyrroles with one as Por, they are denoted as mixed sandwich‐type compounds [68]. The discovery of homogeneous bisphthalocyaninate, Sn(Pc)2, in a double‐decker structure dates from 1936 [69]. This compound has been constructed from the reaction of (Pc)SnCl2 and Na2(Pc). In 1965, the first RE Pcs were discovered by Kirin and Moskalev [70]. The electrochromic behavior of bisphthalocyanine RE compound RE(Pc)2 was demonstrated in 1979 due to the presence of three ligand‐based redox transformations including anionic [(Pc2−)M3+(Pc2−)]−, neutral [(Pc2−)M3+(Pc•−)]0, and cationic [(Pc•−)M3+(Pc•−)]+ forms. The difference in spectrum and the presence of radical of three forms in different colors attracted intense researchers' interest. The definite molecular structure of double‐decker neodymium bisphthalocyaninate, Nd(Pc)2, was revealed by SCXRD technology in 1980 [71].

Figure 1.6 Schematic diagram of sandwich‐type phthalocyanine‐based complexes.

Source: Reproduced from Ref. [67] / with permission of John Wiley & Sons.

The big ionic radii and the high coordination numbers of RE ions ensure the formation of not only the double‐decker but also the triple‐decker metal Pc compounds under optimal reaction conditions. The study of homogeneous tris(phthalocyaninato) RE metal compound was started based on the landmark compound [Y2(Pc)3] in 1986 [72]. In these stacking sandwich‐type complexes, the inter‐macrocycle π‐π interactions make them unique optical and electrochemical properties, and the eight‐coordination geometry of paramagnetic RE metals further expands their applications to the active fields of molecular magnetism and spintronics [73, 74]. Actually, the investigations of the reaction conditions for double‐ and triple‐decker RE compounds have been intensely performed, giving birth to several useful protocols. Generally, the template tetracyclization of phthalonitriles and RE salts mainly yields double‐deckers in high boiling point alcohols with the help of DBU under low temperatures [75]. On the contrary, the reactions between as‐prepared Pcs and metal salts refluxed in high boiling point solvents prefer fabricating the mixture of double‐ and triple‐decker complexes, and high temperatures and long reaction times are helpful for the formation of triple‐decker species. Since 2010, the investigation of the construction, characterization, and properties of multiple‐decker heterometallic (RE/cadmium) complexes made up of four, five, and six tetrapyrrole macrocycles has initiated a new family of sandwich‐type compounds. [76] The double‐decker RE compounds have been used as building blocks to react with cadmium and monomeric Pcs to generate multiple‐decker compounds in 1,2,4‐trichlorobenzene (TCB) [77]. It is worth noting that such double‐deckers were able to directly construct sandwich‐type quadruple‐decker Pc‐based compounds in solid‐phase reactions at high temperatures [78]. Among these multiple‐decker compounds, the electronic coupling between the RE centers and molar absorption coefficients is decreased following the increased number of Pcs, discovering the intramolecular electronic coupling of macrocycles relied on the RE ion size and the super‐distance metal–metal interactions. [79, 80]

The study of heteroleptic sandwich compounds had been started in the early 1990s [81]. The preparation of heteroleptic double‐deckers M(Pc′)(Pc′′) (Pc′ and Pc′′ represent different Pcs) with different Pcs has been performed with the one‐pot reaction of 4‐propoxyphthalonitrile, 4‐tert‐butylphthalonitrile, and lutetium acetate at 290 °C, followed by the tedious column chromatography purification due to the mixed products with similar molecular polarity. Thus far, the reported heterogeneous double‐deckers M(Pc′)(Pc′′) are usually prepared by the reaction of the half‐sandwich Pc compounds and various substituted Pcs. Alternatively, they are obtained by the reaction of half‐sandwich Pcs and phthalonitriles in the presence of DBU. The production yield for these heteroleptic species is usually low due to the generation of homoleptic side products. Triple‐deckers in the form of (Pc′)M1(Pc′′)M2(Pc′) and (Pc′)M1(Pc′)M2(Pc′′) (M1 and M2 could be either the same metal ions or the different metals) could be prepared by the reaction of double‐decker compounds, monophthalocyanine, and RE salt or double‐decker compounds and half‐sandwich‐type compounds in high boiling point solvents. Heteroleptic quadruple‐deckers were fabricated by the complexation of heteroleptic double‐deckers or two different double‐deckers with cadmium ion, where the preferred localization of cadmium is between the two electron‐rich Pcs. It is worth noting that there is an interesting example composed of cadmium metalation of clamshell‐type dimeric Pcs to form sandwich‐type quadruple‐decker complexes [82]. In addition, the fused Pcs connect double‐decker and triple‐decker subunits together to afford heteroleptic binuclear and tetranuclear RE sandwich‐type compounds through the one‐pot and stepwise methods. At the end of this paragraph, the heteroleptic bis(phthalocyaninato) RE double‐deckers are connected by alkali metal ions (such as Na+ and K+ coordination with non‐peripheral octaalkoxy‐substituted and peripheral crown‐substituted Pcs) to generate supramolecular pseudo‐quadruple‐decker compounds (Figure 1.7) [67, 83, 84]. Heterometallic multiple‐decker complexes with up to six decks have been prepared by the homoleptic/heteroleptic double‐deckers to react with cadmium ions and monophthalocyanine in refluxed TCB [85].

Figure 1.7 (a) Crystal structure of terbium(III)‐phthalocyaninato double‐decker complexes with crown moieties and square antiprism (SAP) coordination environment (pink: Tb, gray: C, red: O, blue: N, white: H).

Source: Reproduced from Ref. [83] / with permission of John Wiley & Sons.

Mixed Pc‐based compounds in the form of triple‐decker structure involving phthalocyaninato and porphyrinato ligands were discovered in 1986 [86], which are provided from a refluxed TCB solution of dilithium phthalocyaninate and mono(porphyrinato)‐lanthanide generated from meso‐tetrakis(4‐methoxyphenyl) Por and RE(acac)3 (RE = Nd, Eu, Gd). These triple‐decker compounds were also prepared in modest yields through unseparated RE monoporphyrinates reacting with double‐decker M(Pc)2 in refluxing TCB. The first triple‐decker species, [(Tpp)Ce(Pc)Gd(Oep)], Oep = octaethylporphyrin dianion, composed of both different metals and macrocycles, was reported in 1996, and its molecular structure has been clearly disclosed by SCXRD determination [87]. In contrast, the mixed phthalocyaninato and porphyrinato double‐decker sandwich‐type compounds were obtained later. Their preparation, crystal structures, and spectroscopic properties have been systematically studied with the representative of the neutral [(TPP)RE(Pc)] (TPP and Pc = dianions of tetraphenylporphyrin and Pc, respectively; RE = La, Pr, Nd, Eu, Gd, Er, Lu, and Y in trivalent redox state), which were fabricated by the reaction of dilithium Pc and metal acetylacetonate M(acac)3 and then tetraphenylporphyrin [88]. Similar to the neutral double‐decker Pc RE compounds, they have the characteristic spectroscopic properties of a one‐electron‐oxidized radical‐containing Pc ring (Pc•−). As a result, these radical‐containing Pc rings can be transformed to [(TPP2−)RE(Pc2−)]− and di‐π‐radical [(TPP•−)RE(Pc•−)]+. These different redox states of double‐deckers also influence the behaviors of single‐molecule magnets [89]. In addition, the preparation of mixed (phthalocyaninato)(porphyrinato) double‐deckers was based on the template reaction of the half‐sandwich porphyrinato RE compound with phthalonitrile compounds. Since 2012, the mixed (phthalocyaninato)(porphyrinato) compounds have attracted new interests due to the excellent crystallinity and D4d coordination geometry around paramagnetic lanthanide ions for single molecular magnets [90]. Thus far, there are three forms of mixed triple‐deckers, including [(Por′)M1(Pc′)M2(Por′)], [(Por′)M1(Pc′)M2(Pc′′)], and [(Pc′)M1(Por)M2(Pc′)] [91]. Notably, a mixed (phthalocyaninato)(porphyrinato) quadruple‐decker RE‐Cd compound was derived from the one‐pot reaction of mixed double‐deckers and homoleptic double‐deckers in the presence of cadmium acetate in 2011 [92]. In addition to the homoleptic and heteroleptic Pc‐based compounds and mixed (phthalocyaninato)(porphyrinato) metal complexes, there are few examples where the RE metals are sandwiched between the Pc and other macrocycles, such as corrole [93], N‐confused Por [94], hemiporphyrazine [95], Salen [96, 97], and cyclen ligands [98]. In particular, mixed Pc and Salen metallic compounds have been built in the form of double‐, triple‐, and quadruple‐decker structures.

1.3.2 μ‐Oxo‐Linked Phthalocyanine‐Based Oligomers

μ‐Oxo‐linked oligomers were defined as those compounds with a metal center of Pc and/or other species bridged by a single μ‐oxo atom to generate bi‐, tri‐, and oligonuclear macrocyclic compounds (Figure 1.8) [99]. SiPc species are one of the most well‐known μ‐oxo‐linked Pc‐based oligomers [100]. μ‐Oxo‐linked SiPc dimers are easily formed from a refluxing toluene solution of SiPc(OH)2 in the presence of CaCl2[101]. In addition, various μ‐oxo dimers of metallic Pcs of Al, Ti, Mn, Fe, and Cr metals have been reported [99]. For example, both μ‐oxo diiron unsubstituted and substituted Pcs have been prepared. The first μ‐oxo dimer with a bent Fe‐O‐Fe moiety is capable of being obtained from monomeric iron Pcs in organic solvents (DMF, dimethylacetamide [DMA], tetrahydrofuran, dioxane, and dimethyl sulfoxide [DMSO]) in air [102]. In contrast, the other kind of μ‐oxo dimers with a linear Fe‐O‐Fe moiety has been prepared in either a mixed solution of 96% H2SO4 and 1‐chloronaphthalene or 2‐propaneamine. In addition, they are also fabricated using 96% H2SO4 and then precipitated with water. Since 1999, the catalytic properties of μ‐oxo‐linked iron Pc dimer have been demonstrated toward the oxidation of aromatic compounds to quinones [103], showing superior catalytic properties than the corresponding mononuclear counterparts due to the unique dimeric structure for the former system [99, 104]. Due to the technological development of gel permeation chromatography, μ‐oxo SiPc trimers and tetramers have been successfully purified from the mixture prepared by the condensation products of SiPc(OH)2. This series of μ‐oxo SiPc oligomers has attracted much attention owing to the cofacial macrocyclic π‐conjugation structures with an interplanar distance of 3.3 Å [105]. In addition to the μ‐oxo homoleptic Pc oligomers, there are also heteroleptic Pc and other tetrapyrrole oligomers [106], as well as single μ‐nitrido‐ and μ‐carbido‐linked dimers [107, 108]. Single μ‐nitrido diiron Pcs are constructed from a boiling chloronaphthalene of monomeric iron Pcs or μ‐oxo diiron Pcs reacting with NaN3. These μ‐nitrido diiron Pcs have been used for a series of difficult organic transformations, including oxidation of methane and benzene, transformation of aromatic C–F bonds, oxidative dechlorination, and formation of C–C bonds under clean and mild conditions.

Figure 1.8 General structures of homo‐ and heterometallic complexes in homo‐ and heteroleptic ligand environment.

Source: Reproduced from Ref. [99] / with permission of Elsevier.

1.3.3 Phthalocyanine‐Based Supramolecular Oligomers

Organic synthesis and supramolecular chemistry bring a tight tap between molecular design and the study of Pcs' properties. In these directions, coordination interactions between metals and ligands have been widely used to prepare supramolecular materials. Thus, it is also an important toolkit to construct supramolecular oligomers and polymers based on Pcs. As early as in 1997, homogeneous Pc dimer was formed by metal–ligand interactions between Zn(II) hexaoctylpyridino[3,4]tribenzoporphyrazine derivative [109]. In this study, the metal‐free macrocycle with a yield of 10% was prepared by the reaction of 3,4‐dicyanopyridine with excess 3,6‐dioctylphthalonitrile with the help of C5H11OLi. The asymmetric Pc monomer contains three isoindolic moieties and a pyridine (py) unit in refluxing pentanol, forming edge‐to‐face dimer through the complexation of the py moiety with zinc atom from another compound in the axial direction. In contrast, the replacement of zinc ion with nickel ion only leads to face‐to‐face aggregates. The similar coordination‐bonded dimers composed of py unit‐containing Pc compounds have been studied by other groups [110, 111] (Figure 1.9). These dimeric compounds have been explored using electronic absorption spectroscopy, fluorescence spectroscopy, magnetic circular dichroism spectroscopy, and time‐resolved electron paramagnetic resonance spectroscopy.

Figure 1.9 Zn(II) pyridino[3,4]tribenzoporphyrazine and two modes of self‐assemblies.

Source: Adapted from Refs. [3, 4].

Most of the Pc‐based supramolecular structures based on coordination bonding interactions involve the Zn(II) and Ru(II) species. In 2005, hexa‐n‐butoxyimidazolylphthalocyaninato zinc compound was constructed through the condensation between 6‐cyanodiiminoisoindoline and excessive 6,7‐dibutoxydiiminoisoindoline with the assistance of Zn(OAc)2 (Figure 1.10) [112]. Its cyan group is further reacted with N‐methylethylenediamine to form an imidazolinyl substituent followed by oxidation of the imidazolinyl derivative with 5% Pt/C to form zinc hexa‐n‐butoxyimidazolylphthalocyanine. In addition, 2‐(1‐methyl‐2‐imidazolyl)‐9(10),16(17),23(24)‐tri‐tert‐butylphthalocyaninato zinc and 2‐(1‐methyl‐2‐imidazolyl)‐9(10),16(17),23(24)‐tri‐tert‐butylphthalocyaninato magnesium were prepared using the similar method. The self‐association behaviors of these compounds have been checked by titrations in toluene using ultraviolet‐visible (UV–vis) spectroscopy, revealing a large association constant of 1.4 × 1011 ∼ 1.1 × 1012 M−1. The nuclear magnetic resonance spectroscopy (NMR) results disclose the formation of the J‐type Pc dimers, exhibiting excellent fluorescence. In 2000, a Pc pentamer was prepared through a one‐step reaction of oxo(phthalocyaninato)titanium(IV) with 2,3,9,10,16,17,23, 24‐octahydroxyphthalocyanine. The obtained compound was characterized by mass, electronic absorption, and magnetic circular dichroism spectroscopy [113].

Figure 1.10 Synthesis procedures of hexa‐n‐butoxyimidazolynylphthalocyaninato zinc and hexa‐n‐butoxyimidazolylphthalocyaninato zinc.

Metal–ligand supramolecular oligomers made up of Pcs and other photoactive species have been assembled through coordination bonds, forming various donor–acceptor (D‐A) systems for exploring their basic chemistry and photophysics. Ru(II) compounds show remarkable stability in solutions due to the robust metal–pyridyl connection. Due to the absence/presence of terminal CO complexation, mononuclear Ru(II)Pc precursors are coordinated with either one or two sides in the axial position, leading to the photoactive dinuclear and trinuclear D‐A species. For instance, pyridyl‐containing perilendiimides (PDIs) and fullerene (C60) have been used to coordinate with Ru(II) macrocycles, forming D‐A dimeric and trimeric compounds [23,114–116]. In 2006, a novel donor–acceptor–donor (D‐A‐D) trimer hybrid was constructed by the axial complexation of two metallic Pcs [Ru(CO)Pc] with a PDI linker containing two 4‐pyridyl substituents. [Ru(CO)Pc] was prepared by through the metalation of the tetra‐tert‐butylphthalocyanine to react Ru3(CO)12 in refluxing phenol with a yield of 80%. In addition, a PDI linker bearing two 4‐pyridyl groups located on the imido position was produced by the reaction of 1,7‐bis(3′,5′‐di‐tert‐butylphenoxy)perylene‐3,4:9,10‐tetracarboxydianhydride with 4‐ aminopyridine with the help of Zn(OAc)2. Single carbonyl coordination [Ru(CO)Pc] ensures the complexation of one PDI linker at the opposite axial site of two Pc molecules with a yield of 68% in chloroform. These monomeric compounds and trimeric arrays have been characterized by various spectroscopic methods. The photophysical properties of this D‐A compound were determined, revealing the photo‐driven generation of the long‐lived radical ion pair states [Ru(CO)Pc•+‐BPyPDI•−‐Ru(CO)Pc] with a lifetime of 115 ns.

In 2016, new cart‐wheel‐type D‐A‐D hybrids were constructed by modifying the metals and peripheral substituents of Pcs and PDI for optimizing their photophysical behaviors (Figure 1.11) [115]. In addition to zinc/ruthenium carbonyl tetra‐tert‐butylphthalocyanine regioisomers, Zn(II) and Ru(II) Pc derivatives containing four and eight ferrocenes attached on the peripheral positions of macrocycles were prepared for constructing D‐A‐D hybrids. Suzuki cross‐coupling reaction between 4‐iodophthalonitrile and ferroceneboronic acid generated 4‐ferrocenylphthalonitrile with a yield of 45%. The subsequent template cyclotetramerization of this precursor led to the formation of four ferrocene‐substituted zinc/metal‐free Pcs. Another analog ruthenium carbonyl Pc was prepared through the metalation of metal‐free Pc and ruthenium dodecacarbonyl with a yield of 24%. For easy characterization and comparative study, symmetric octa‐substituted metallic Pcs were also prepared. Therefore, 4,5‐bisferrocenylphthalonitrile was afforded using Suzuki cross‐coupling between 4,5‐diiodophthalonitrile and ferroceneboronic acid. However, the electron‐donating effect of ferrocene units prevents the successful template cyclotetramerization based on the above‐described cyclotetramerization conditions. Instead, cyclotetramerization of the corresponding diiminoisoindolines was achieved with the help of hexamethyl disilazane, and the necessary metalation was employed to provide ruthenium carbonyl octa‐substituted Pc. N,N′‐Di(4‐pyridyl)‐1,6,7,12‐tetrakis(4′‐tert‐butylphenoxy)perylene‐3,4:9,10‐tetracarboxylic acid bisimide [BPyPDI] was reacted with an excess of ruthenium carbonyl complexes in chloroform at room temperature to obtain the D‐A‐D trimers with a yield of 58–78%. The complexation of zinc Pc and BPyPDI in chloroform was carefully explored using the NMR technique. In particular, electronic communications between ferrocene units through Pc macrocycle (long distance across 11 bonds) were observed, and tiny electronic communications were also indicated between the Pc and PDI chromophores. Furthermore, the introduction of ferrocenes facilitates the fast energy transfer from the excited‐state PDI to Pcs. In addition, these ferrocene substituents slightly accelerate the charge separation of the RuPc–PDI arrays upon photoexcitation of the PDI chromophore but significantly speed up charge recombination. Similar assembly and photophysical studies have been performed upon Pc‐C60 supramolecular arrays made up of linear fullerene mono‐ and bispyridyl ligands to zinc/ruthenium Pcs [114, 116]. In addition to the coordination‐driven oligomers, there are also supramolecular arrays constructed from Pc and functional chromophores through other weak interactions, such as hydrogen bonds and crown ether–alkyl ammonium cation interactions [117–120]. In this chapter, those supramolecular nanostructures including nanowires and nanoparticles, which are obtained from the self‐assembly process and seem to have no well‐defined structures, are not discussed due to lack of well‐defined structures.

1.3.4 Phthalocyanine‐Based Covalent‐Bonded Oligomers

1.3.4.1 Phthalocyanine‐Based Fused Oligomers