Terpyridine-based Materials E-Book

Ulrich S. Schubert

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

Seitenzahl: 889

Veröffentlichungsjahr: 2012

Beschreibung

In recent years, the utilization of terpyridines both in macromolecular structure assembly and device chemistry has exploded, enabling, for
example, supramolecular polymer architectures with switchable chemical and physical properties as well as novel functional materials
for optoelectronic applications such as light-emitting diodes and solar cells. Further applications include the usage of terpyridines and their
metal complexes as catalysts for asymmetric organic reactions and, in a biological context, as anti-tumor agents or biolabels. This book covers terpyridine-based materials topics ranging from syntheses, chemistry, and multinuclear metal complexes, right up to functionalized polymers, 3D-architectures, and surfaces. Aimed at materials scientists, (in)organic chemists, polymer chemists, complex chemists, physical chemists, biochemists, and libraries.

Leseprobe

Contents

Preface

List of Abbreviations

Chapter 1: Introduction

Chapter 2: Synthesis, Properties, and Applications of Functionalized 2,2′:6′,2″-Terpyridines

2.1 Introduction

2.2 Basic Synthetic Strategies

2.3 Synthesis and Properties of 2,2′:6′,2″-Terpyridine Derivatives

2.4 2,2′:6′,2″-Terpyridines Symmetrically Substituted on the Outer Pyridine Rings

2.5 Ziessel-Type 2,2′:6′,2″-Terpyridines

2.6 Kröhnke-Type 2,2′:6′,2″-Terpyridines

2.7 Miscellaneous Terpyridine-Analogous Compounds

Chapter 3: Chemistry and Properties of Terpyridine Transition Metal Ion Complexes

3.1 Introduction

3.2 Basic Synthetic Strategies and Characterization Tools

3.3 Ru II and Os II Complexes

3.4 Iridium(III) Complexes with Terpyridine Ligands

3.5 Platinum(II) Mono(terpyridine) Complexes

Chapter 4: Metallo-Supramolecular Architectures Based on Terpyridine Complexes

4.1 Introduction

4.2 Terpyridine-Containing Metallo-Macrocycles

4.3 The HETTAP Concept

4.4 Racks and Grids

4.5 Helicates

4.6 Rotaxanes and Catenanes

4.7 Miscellaneous Structures

Chapter 5: π-Conjugated Polymers Incorporating Terpyridine Metal Complexes

5.1 Introduction

5.2 Metallo-Supramolecular Polymerization

5.3 Metallopolymers Based on π-Conjugated Bis(terpyridine)s

5.4 Main-Chain Metallopolymers Based on Terpyridine-Functionalized π-Conjugated Polymers

Chapter 6: Functional Polymers Incorporating Terpyridine-Metal Complexes

6.1 Introduction

6.2 Polymers with Terpyridine Units in the Side-Chain

6.3 Polymers with Terpyridines within the Polymer Backbone

Chapter 7: Terpyridine Metal Complexes and their Biomedical Relevance

7.1 Introduction

7.2 Terpyridine Metal Complexes with Biological Activity

Chapter 8: Terpyridines and Nanostructures

8.1 Introduction

8.2 Terpyridines and Surface Chemistry

8.3 Terpyridines and Inorganic Nanomaterials

8.4 Terpyridines and Nano-Structured TiO 2: Photovoltaic Applications

8.5 Organopolymeric Resins, Beads, and Nanoparticles

Chapter 9: Catalytic Applications of Terpyridines and Their Transition Metal Complexes

9.1 Introduction

9.2 (Asymmetric) Catalysts in Organic Reactions

9.3 Electrocatalytic Oxidation and Reduction Processes

9.4 Photocatalytic Processes

Chapter 10: Concluding Remarks

Index

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The Authors

Prof. Dr. Ulrich S. Schubert

Friedrich-Schiller-University Jena

Laboratory of Organic and Macromolecular Chemistry (IOMC) and Jena Center for Soft Matter (JCSM)

Humboldtstr. 10

07743 Jena

Germany

Dr. Andreas Winter

Friedrich-Schiller University Jena

Laboratory of Organic and Macromolecular Chemistry (IOMC) and Jena Center for Soft Matter (JCSM)

Humboldtstraße 10

07743 Jena

Germany

Prof. Dr. George R. Newkome

The University of Akron

Departments of Polymer Science and Chemistry & The Maurice Morton Institute of Polymer Science

Akron, OH, 44325-4717

USA

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2011 Wiley-VCH Verlag & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany

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Preface

Over the past few decades, supramolecular chemistry, that is, the self-assembly of molecules into complex architectures based on weak secondary interactions (e.g., metal-to-ligand coordination or hydrogen bonding), has evolved from a primary scientific field into daily-life applications. In particular, the combination of transition metal ions with N-heteroaromatics, as ligands, has rapidly moved to the center of attention in laboratories around the world. As one of the most prominent representatives of this family, terpyridine was discovered in 1931 and has been shown to lend itself to the construction of specific, stable metal complexes with unique properties that can easily be tuned by the choice of the metal ion and/or the structural modification. An overview of the syntheses and early applications of the parent and substituted 2,2′:6′,2″-terpyridines was given in the book Modern Terpyridine Chemistry in 2006. The emerging applications in the fields of polymer science, optoelectronic devices, medicinal chemistry, nanotechnology, and molecular catalysis prompted us to review the utilization of terpyridine-based materials in more detail and with respect to current applications.

We have attempted to compile the key examples in each field to assist and help future researchers in this arena; many excellent examples are available and support the rationale for continued exploitation of this family of heterocyclic compounds, but we must admit that not all of them could be chosen due to space constraints. Therefore, we apologize in advance to those authors whose work has not been incorporated.

The authors would be, as always, most grateful to know of any errors, which may have crept into the manuscript despite the multiple proofreading by many of our colleagues. We also thank our spouses, relatives, and friends for their patience and assistance in completing this work.

Jena and Akron, July 2011

Ulrich S. Schubert

Andreas Winter

George R. Newkome

List of Abbreviations

A2780human ovarian carcinoma cellsA-498human kidney carcinoma cellsA-549human lung carcinoma cellsAASatomic absorption spectroscopyacacacetylacetonateACIaverage current intensityAFMatomic force microscopyAIBN2,2′-azobisiso-butyronitrileAlq3tris(8-hydroxyquinoline)aluminumAPaminopentanolAPCEabsorbed photon-to-current efficiencyATRPatom-transfer radical polymerizationAUCanalytical ultracentrifugationBAbutyl acrylateBCPbond critical pointBEL-7420human hepato carcinoma cellsBGC-823human gastric gland carcinoma cellsBINOL1,1′-binaphth-2-olbip2,6-bis(1-methyl-1H-benzo[d]imidazol-2-yl)pyridinebip-OH2,6-bis(1-methyl-1H-benzo[d]imidazol-2-yl)pyridin-4-olbmim-PF61-butyl-3-methylimidazolium hexafluorophosphateBNCTboron neutron capture therapyBODIPYboron-dipyrrometheneBPGbasal plane pyrolytic graphitebpm2,2′-bipyrimidinebpp1,4-bis(2,6-di(1H-pyrazol-1-yl)pyridin-4-yl)benzenebpy2,2′-bipyridinebpz2,2′-bipyrazineBSAbovine serum albuminBTBbipyridine-terpyridine-bipyridinebtp1,4-bis(2,6-bis(1-butyl-1H-1,2,3-triazol-4-yl)pyridin-4-yl)-benzene or 4,4′-di(tert-butyl)-2,2′-bipyridine or 2,6-bis(1H-1,2,3-triazol-4-yl)pyridine(s)btpyan1,8-bis(2,2′:6′,2“-terpyridin-4-yl)anthracenebzimpy2,6-bis(benzimidazol-2-yl)pyridineC13human ovarian carcinoma cellsCALBlipase B from Candida antarcticaDACdeoxycholic acidCCAACCuI-catalyzed alkyne-azide cycloaddition (reaction)CCD19Luhuman normal pulmonary cellCDcircular dichroismCDIN,N′-carbonyldiimidazoleCFScompetitive fluorescence spectroscopyCH1human larynx and pharynx cancerCIECommision International d’EclairageCITScurrent imaging tunneling spectroscopyC^N^Nmono-cyclometalating tridentate (ligand)CNTcarbon nanotubeCODcycloocta-1,5-dieneCRPcontrolled radical polymerizationcryo-TEMcryogenic transition electron microscopyCScharge-separatedCSFcompetitive fluorescence spectroscopyctcalf thymusCTcharge-transferCTAchain-transfer agentCVcyclic voltammetryCVPchemical vapor depositionCystcystineCyt-ccytochrome-cCzMA2-(N-carbazolyl)ethyl methacrylatedbadibenzylideneacetoneDCAdeoxycholic acidDEDTCdiethyldithiocarbamateDFTdensity functional theoryDHPdi(hexadecyl)phosphate or 1,4-dihydropyridinediaddi(iso-propylazo)dicarboxylateDLSdynamic light scatteringdmbpy4,4′-dimethyl-2,2′-bipyridineDMF or dmfN,N-dimethylformamideDMPO5,5-dimethyl-1-pyrroline-N-oxideDMSO or dmsodimethylsulfoxideDNAdeoxyribonuleic acidDOSYdiffusion-ordered spectroscopy (NMR)DPdegree-of-polymerizationD-P-Adonor-photosensitizer-acceptor (array)dpp2,4-di(pyridin-2-yl)pyrazolate or 2,9-diphenyl-1,10-phenanthrolinedppenecis-1,2-bis(diphenylphosphino)ethylenedppf1,1′-bis(diphenylphosphino)ferroceneDPVdifferential pulse voltammetrydpbq8,8′-diphenyl-3,3′-biisoquinolinedpp2,9-diphenyl-1,10-phenanthrolinedppf1,1′-bis(diphenylphosphino)ferrocenedppt5,6-diphenyl-3-(phenanthrolin-2-yl)-1,2,4-triazinedppzdipyrido[3,2-a:2′,3′-c]phenazinedppzp6′-(2″-pyridyl)dipyrido[3,2-a:2′,3′-c]phenazineDSdegree-of-substitutionDSBdouble-strand breakDSCdifferential scanning calorimetryDSSCdye-sensitized solar cellDTCdithiocarbamateDTEdithienyletheneE0-0zero-zero spectroscopic energyEDAethyl diazoacetateEDOT3,4-ethylenedioxythienylEDTAethylenediaminetetraacetic acidEHMOextended Hückel molecular orbitalEIelectron ionization (mass spectrometry)EF(luminescence) enhancement factorELelectroluminescenceemim-I1-ethyl-3-methylimidazolium iodideEPMAelectron probe microanalysis (spectrum)EPRelectron paramagnetic resonance (spectroscopy)EPTelectron/proton-transferESIelectrospray ionizationETelectron-transferEthBrethidium bromideEVSA-Thuman breast cancer cellsEWGelectron-withdrawing groupFcferroceneFFfill factorFIDfluorescent intercalator displacementFSFremy’s salt (potassium nitrosodisulfonate)FTICRFourier-transform ion cyclotron resonanceFTOfluorine-doped tin oxideFWHMfull width at half maximumGlyglycineGMPguanosine 5′-monophosphateGRglutathione reductaseGSground stateGSHglutathioneH226human non-small lung cancer cellsHBChexa-peri-hexabenzocoroneneHCT-116, -15human colon adenocarcinoma cellsHEEDTAsodium salt of N-hydroxyethylethylenediamine triacetic acidHeLacervical cancer cells from Henrietta LacksHepG2human liver carcinoma cellHEThelix-extension (parameter)HETPHENheteroleptic phenanthroline (complexation)HETTAPheteroleptic terpyridine and phenanthroline (complexation)HL-60human promyelocytic leukemia cellsHOMOhighest occupied molecular orbitalHOPGhighly-ordered pyrolytic graphiteHShigh-spin (state)HSAhuman serum albuminHT-29human colon adenocarcinoma cellsHTelohuman telomeric (DNA sequence)hTrxthioredoxinhTrxRthioredoxin reductaseHWEHorner-Wadsworth-Emmons (condensation reaction)Iscshort circuit currentIC50half maximal inhibitory concentrationICPinductively coupled plasma (mass spectrometry)IDAinterdigitated (microelectrode) arrayIETinterfacial electron transferIGROVhuman ovarian carcinoma cellsILintraligandILCTintraligand charge-transferIPCEincident photon-to-current conversion efficiencyIREiron regulatory elementITCisothermal titration calorimetryITEinterfacial electron transferITOindium tin oxideJcurrent densityKBhuman epidermoid cancer cellsKBbinding constantK0ion-free binding constantKSVStern-Volmer constantLluminanceL1210murine leukemia cellLASlight absorption sensitizerLBLangmuir-BlodgettLBLlayer-by-layerLCligand-centered or liquid crystallineLCSTlower critical solution temperatureLDlinear dichroism (spectroscopy)LDAlithium di(iso-propyl)amideLFlactoferrinLHElight harvesting efficiencyLIESSTlight-induced excited-state spin-trappingLLCTligand-to-ligand charge-transferL/L0relative contour lengthLSlow-spin (state)LUMOlowest unoccupied molecular orbitalM19 MELhuman melanoma cellsMALDI-TOFmatrix-assisted laser desorption/ionization time-of-flight (mass spectrometry)MCmetal-centeredMCF-7human breast cancer cellsmCPBAm-chloroperbenzoic acidMeCNacetonitrileMeCysS-methylcysteineMEFmetal-enhanced fluorescenceMEMSmicro-electro-mechanical systemsMEPEmetallo-supramolecular polyelectrolytesmes2,4,6-trimethylphenyl (mesityl)MFmelamine formaldehydeMLCTmetal-to-ligand charge-transferMLLCTmetal-ligand-to-ligand charge-transferMMAmethyl methacrylateMMMmolecular monolayer memory (device)MMNVMmolecular monolayer non-volatile memory (devices)Mnnumber-average molar massMOmolecular orbitalMPEGpoly(ethylene oxide) monomethyl etherMRImagnetic resonance imagingMSmass spectrometryMV2+1,1′-dimethyl-4,4′-bipyridinium, methyl viologenMWmolecular wireMWNTmulti-walled carbon nanotubesNCI-H460human lung carcinoma cellsNDRnegative differential resistanceNEMN-ethylmorpholineNHEnormal hydrogen electrodeNLOnon-linear opticsNMPnitroxide-mediated polymerization orN-methylpyrrolidoneNMRnuclear magnetic resonance (spectroscopy)N^Nbidentate N-heteroaromatic ligandN^N^Ntridentate (ligand)ODNoligodeoxynucleotideODTn-octadecanethiolOEGMAoligo(ethylene oxide) methacrylateOHToligohexylthiopheneOLoptical limiterOLEDorganic light-emitting diodeOPEoligo(p-phenylene-ethylene)OPVoligo(phenylenevinylidene)ORTEPOak Ridge thermal-ellipsoid plotOSCorganic solar cellsP2VP/P4VPpoly(2-vinylpyridine)/poly(4-vinylpyridine)P-388human leukemia cell linesP3HTpoly(3-hexylthiophene)PAApoly(acrylic acid)PACpolyelectrolyte-amphiphile complexpbpy6-phenyl-2,2′-bipyridinePC-3human prostate adenocarcinoma cellsPCBM[6,6]-phenyl-C61-methyl butyratePCDpoly(chloromethylstyrene-co-divinylbenzene)PCETproton-coupled electron-transferPCLpoly(ε-caprolactone)PDAphoto-diode arrayPDIperylene diimidePDMAApoly(N,N-dimethyl-acrylamide)PDMSpoly(dimethylsiloxane)PEBpoly(ethylene-co-butylene)PECphotoelectrochemicalPEGpoly(ethylene glycol)PEIpoly(ethylene imine)PEDOTpoly(3,4-ethylenedioxythiophene)PEtOxpoly(2-ethyloxazoline)PETphotoinduced electron-transferPFDSpoly(ferrocenyldimethylsilane)phen1,10-phenanthrolinephi9,10-phenanthrenequinone diiminePIpolyisoprenepiaphotoinduced absorptionPLphotoluminescencePLApoly(L-lactide)PLEDpolymer light-emitting diodePMDETAN,N,N,N“,N“-pentamethyldiethylenetriaminePMMApoly(methyl methacrylate)PNIPAMpoly(N-isopropylacrylamide)POMpolarized optical microscopy or polyoxometalatePPFSpoly(pentafluorostyrene)PPGpoly(propylene glycol)PPVpoly(p-phenylenevinylidene)PSpoly(styrene)PSCpolymer solar cellPSCApotential-step chronoamperometrypslpostsynthetic labelingPSSpoly(styrene sulfonate)PTFMSpoly(4-trifluorometylstyrene)PTHFpoly(tetrahydrofuran)PURpolyurethanePVphotovoltaicPVCpoly(vinylchloride)PVDphysical vapor depositionpydicpyridine-2,6-dicarboxylic acidQCM-Dquartz crystal microbalance with dissipation (monitoring)QCRquartz crystal resonatorQGY-TR50human hepatocellular carcinoma cell lineQQNquasi-quadratic networkQTAIMquantum theory of atoms in moleculesququinolineRAFTreversible addition-fragmentation chain-transfer polymerizationRhhydrodynamic radiusRNAribonucleic acidROESYrotating-frame Overhauser effect spectroscopyROMPring-opening metathesis polymerizationROPring-opening polymerizationRPTEChuman normal cell lineSAMself-assembled monolayerSAMLself-assembled multilayerSANSsmall angle neutron scatteringSAXSsmall angel X-ray scatteringSCspin-crossoverSCEstandard calomel electrodeSECsize exclusion chromatographySEMscanning electron microscopySF-268glioblastoma cell linesSGC-7901human gastric carcinoma cellsSHEstandard hydrogen electrodeSHGsecond-harmonic generationSIMSsecondary ion mass spectrometrySK-MEL-2human skin melanoma cellsSKOV-3human ovary adenocarcinoma cellsSmCsmectic C (phase)SMMsingle molecule magnetSPANsulfonated polyanilineSPGschizophyllanSPMscanning probe microscopySPSsurface plasmon spectroscopy or solid-phase synthesisSSBsingle-strand breakSTMscanning tunneling microscopySUNE-1human nasopharyngeal carcinoma cellsSWNTsingle-walled carbon nanotubeTtemperaturetaz3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazoleTBAPtetra(n-butyl)ammonium hexafluorophosphateTBTterpyridine-bipyridine-terpyridineTDtime-dependentTEAtriethylamineTEGtetra(ethylene glycol)TEMtransmission electron microscopyTEMPO2,2,6,6-tetramethylpiperidinyl-1-oxylTEOAtriethanolamineTEOStetraethoxysilaneTFAtrifluoroacetic acidTgglass transition temperatureTGAthermal gravimetric analysisTHFtetrahydrofuranTHzterahertz (spectroscopy)TIPNO2,2,5-trimethyl-4-phenyl-3-azahexane nitroxideTmmelting tempoeratureTMP2,2,6,6-tetramethylpiperidineTP+2,4,6-triarylpyridiumtppz2,3,5,6-tetra(pyridin-2yl)pyrazinetptztris(pyridin-2-yl)triazinetpy2,2′:6′,2″-terpyridineTRtrypanothione reductasetpy-PO(OH)22,2′:6′,2“-terpyridin-4′-yl-phosphonic acidtpy-SPGterpyridine-modified schizophyllanttpy4′-tolyl-2,2′:6′,2″-terpyridineTWIMtravelling wave ion mobility (MS)tppz2,3,5,6-tetrakis(pyridin-2-yl)pyrazineUCSTupper critical solution temperatureUPyureidopyrimidinoneVocopen circuit voltageWAXDwide angle powder X-ray diffractionWIDRhuman colon carcinoma cellsWOLEDwhite organic light-emitting diodeWRERwrite-multiple read-erase-multiple readXASX-ray absorption spectroscopyXPSX-ray photoelectron spectroscopyXRDX-ray diffractionεelipticyηoverall power conversion efficiency or cell efficiencyεrrelative permittivity valueΦPLphotoluminescence quantum yieldΦPVphotovoltaic quantum yieldτnelectron lifetimesξMmolar susceptibility2VP2-vinylpyridine4VP4-vinylpyridine

Chapter 1

Introduction

In 1987, J.-M. Lehn, C.J. Pedersen, and D.J. Cram were honored with the Nobel Prize in Chemistry for their work on selective host–guest chemistry [1–3]. Since then, supramolecular chemistry has evolved into one of the most active fields within today’s research community. This concept has been delineated by Lehn [4]:

“supramolecular chemistry may be defined as ‘chemistry beyond the molecule’ and is based on organized entities of higher complexity that result from the association of two or more chemical species held together by intermolecular forces.”

Self-recognition and self-assembly processes represent the basic operational components underpinning supramolecular chemistry in which interactions are mainly non-covalent in nature (e.g., van der Waals, hydrogen bonding, ionic or coordinative interactions). In general, these interactions are weaker and usually reversible when compared to traditional covalent bonds. Nature itself represents the ultimate benchmarks for the design of artificial supramolecular processes. Inter- and intramolecular non-covalent interactions are of major importance for most biological processes such as highly selective catalytic reactions and information storage [5]; different non-covalent interactions are present in proteins, giving them their specific structures. DNA represents one of the most famous natural examples, where self-recognition of the complementary base-pairs by hydrogen bonding leads to the self-assembly of the double helix. Starting with the development and design of crown ethers, spherands, and cryptands, modern supramolecular chemistry depicts the creation of well-defined structures via self-assembly processes [6] (similar to the well-known systems found in Nature [7]).

One of the most important interactions applied in supramolecular chemistry is metal-to-ligand coordination. In this arena, chelate complexes derived from N-heteroaromatic ligands, in particular based on 2,2′-bipyridine, 1,10-phenanthroline, and 2,2′:6′,2″-terpyridine (Figure 1.1), have become an ever-expanding synthetic and structural frontier.

Figure 1.1 General structures of 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), and 2,2′:6′,2″-terpyridine (tpy).

Bipyridine has been known since 1888 when Blau first reported the formation of a bipyridine–iron complex [8]. One year later, Blau also synthesized and analyzed bipyridine by dry distillation of copper picolinate [9]. Since this parent molecule consists of two identical parts, no directed coupling procedure is required for its construction. Therefore, unsubstituted and symmetrically substituted, in particular 4,4′-functionalized, bipyridines are readily accessible in good yields by simple coupling procedures [10, 11]. Apart from this, their transition metal (in particular RuII) complexes [12–14] feature interesting photochemical properties, making them ideal candidates for solar energy conversion, for example, in photovoltaic devices [15–23] and light-emitting electrochemical cells [24–28]. The chemistry of 2,2′:6′,2″-terpyridines (often referred to as simply terpyridine or tpy; the other structural isomers are duly noted but not considered further herein) is much younger than that of 2,2′-bipyridines. About 80 years ago, terpyridine was isolated for the first time by Morgan and Burstall by a process in which pyridine was heated (340 °C) in the presence of anhydrous FeCl3 in an autoclave (50 atm) for 36 h [29, 30]; the parent terpyridine was isolated along with a myriad of other N-containing products. It was subsequently discovered that the addition of FeII ions to a solution of diverse terpyridines gave rise to a purple color indicative of metal complex formation.

Since this pioneering work, the chemistry of terpyridine remained merely a curiosity for nearly 60 years, at which point its unique properties were incorporated into the construction of supramolecular assemblies. Terpyridines and their structural analogs have gained much interest in the last two decades as functional templates in the fields of supramolecular and coordination chemistry as well as in materials science [31–38]. This is expressed by the enormous number of scientific publications and patents dealing with the synthesis, properties, and applications of terpyridine-containing systems (March 2011: about 5950 hits in SciFinder™, Figure 1.2). The terpyridine unit contains three nitrogen atoms and can, therefore, act as a tridentate ligand [39, 40]. The rich coordination chemistry and high binding affinity towards various interesting transition as well as rare earth metal ions, in concert with the resulting redox and photophysical properties, have given rise to diverse metallo-supramolecular architectures and a multitude of potential applications. Owing to their distinct photophysical, electrochemical, catalytic, and magnetic properties, terpyridines and their complexes have been studied regarding a wide range of potential applications covering light-into-electricity conversion [16, 41–60], light-emitting electrochemical cells (LECs) [61, 62], (electro)luminescent systems (e.g., organic light-emitting diodes) [63–68], and nonlinear optical devices [69–78]. Moreover, ditopic and dendritic terpyridine ligands may form polymetallic species, which can then be utilized as luminescent or electrochemical sensors [79–134]. Besides these objectives, their biomedical and pharmaceutical utilizations (e.g., as DNA binding or antitumor active agents) are currently rapidly growing fields of research [79, 135–146].

Figure 1.2 Histogram of the number of publications containing the term “terpyridine” using SciFinder™ (the search was performed on 1st March 2011).

Furthermore, the catalytic activity of terpyridines and their transition metal complexes has been employed to enhance various (asymmetric) organic transformations [147–149]: carbon–carbon single bond formation [150], etherification [151], oxidation of alcohols or ethers [152, 153], cyclopropanation [154, 155], epoxidation [156], CuI-catalyzed alkyne-azide cycloaddition (CCAAC) [157], hydrosilylation [158], and controlled radical polymerization to name only a few [159]. Additionally, RuII bis(terpyridine) complexes have also been used for the photocatalytic splitting of water [160–162].

Well-designed supramolecular (co)polymer architectures have been realized, based on the metal-terpyridine connectivity, opening up avenues to smart “self-healing” materials with the opportunity of switching the physical and/or chemical properties of materials depending on parameters such as pH value or temperature [36, 38, 163–173]. Finally, the self-assembly of terpyridine complexes onto nanostructures (e.g., based on gold, silver, CdS, TiO2, carbon nanotubes) [174–178] as well as surfaces (e.g., glass, indium tin oxide, gold, graphite) [179–187] is considered in this context.

The diversity of applications related to terpyridines and their metal complexes calls for a high structural variability of the basic 2,2′:6′,2″-terpyridine subunit. In particular, terpyridine designs featuring π-conjugated substituents, commonly attached in 4′-position, are of increasing interest. Figure 1.3 depicts the general schematic structures of four widely used types of terpyridines. Terpyridines (1) can be considered as “workhorses” in the field of metallo-supramolecular chemistry – a multitude of terpyridine-functionalized polymers has been derived from this structural motif [36, 38, 166, 171, 188, 189]. By far, most conjugated terpyridine-containing systems used today are based on the so-called Kröhnke-motif, which features a functionalized phenyl moiety at the 4′-position of the terpyridine unit (2) [37]. Their rigid U-shaped counterparts 3 have – mainly due to synthetic limitations – been employed less frequently [190] but offer entrée to a more rigid configuration. The Ziessel-type terpyridines 4, where π-conjugation is extended via ethynyl-based systems, have been studied in particular with respect to electron-transfer processes [187, 191].

Figure 1.3 Chemical structures of 4′-functionalized (1, X = O, N or S), a Kröhnke-type (2), a rigid U-shaped (3, n = 0, 1 or 2), and a Ziessel-type terpyridine (4).

In view of the notable importance of 2,2′:6′,2″-terpyridines and their metal complexes in current research, we herein focus on architectures containing these types of ligand and their corresponding metal complexes.

The earlier book Modern Terpyridine Chemistry aimed mainly to summarize the syntheses, chemistry, and properties of functional terpyridine architectures: complexes, supramolecular polymers, 3D-structures, and surfaces [192]. Owing to the fast development of terpyridine-based materials, this book presents a detailed look beyond the basic concepts of syntheses and properties to applications with relevance to various aspects of human life. Therefore, this book consists of different topics related to “terpyridine-based materials,” each of which is discussed in an individual chapter.

Chapter 2 summarizes the known synthetic strategies leading to different terpyridines. Since terpyridines of types 1–4 currently represent the most valuable derivatives, emphasis is laid on the discussion of the various routes of their syntheses. In this context, their properties, in particular their photophysical behavior, is also evaluated.

Chapter 3 describes the preparation and properties of mononuclear terpyridine metal complexes. Emphasis will be on bis(terpyridine) complexes of RuII, OsII, IrIII, and PtII ions as well as their photophysical and electrochemical properties. Moreover, oligonuclear complexes, such as dyads and triads, are included. In particular, architectures based on RuII ions are featured in which combinations with other transition metal ions could, for example, potentially lead to “molecular switches” opening up avenues to the construction of nanodevices.

Chapter 4 features more advanced supramolecular aggregates composed of terpyridine-metal subunits: macrocycles, grids, helicates, or rotaxanes. Such materials are of interest for the understanding of supramolecular aggregation into 2D and 3D architectures. Furthermore, applications as either “molecular machines” or optoelectronic devices have been envisioned.

The combination of π-conjugated bis(terpyridine)s with transition metal ions affords high molar mass π-conjugated metallopolymers; in these materials, the properties of conventional conjugated polymers and terpyridine complexes are merged (Chapter 5). Polymer light-emitting diodes (PLEDs) or polymer solar cells (PSCs) are the most prominent targets of research in this emerging field.

Polymeric architectures containing terpyridine systems with various architectures, from side-chain-functionalized polymers to main-chain metallopolymers, are summarized in Chapter 6. The incorporation of terpyridine complexes into polymer architectures enables the synthesis of advanced multiblock copolymers (that, for instance, can form micelles or phase-separate in the bulk) or polymer-bound photoactive metal complexes for optoelectronic applications.

Chapter 7 summarizes terpyridine metal complexes that have recently found application in the fields of biochemistry and pharmacy. In particular, PtII mono (terpyridine)s are potential cytotoxic agents that could be potential replacements for the traditional PtII-based drugs (e.g., cisplatin, carboplatin). Oxidative DNA cleavage, induced by various types of terpyridine complexes, is another major field in the biomedical arena. Photoluminescent complexes can be attached to biomolecules and, therewith, be utilized as labeling agents in pharmaceutical applications.

The covalent binding of terpyridines to surfaces has led to the development of molecular wires. Fast energy-transfer processes along these wires point to potential applications in organic electronics. Besides their attachment to surfaces, the binding of terpyridine ligands (or their complexes) to organic as well as inorganic nanomaterials will, then, be considered in Chapter 8.

Chapter 9 describes applications of terpyridines and their complexes in the fields of organometallic catalysis. Terpyridine ligands (and their complexes) have been used as homogeneous or heterogeneous catalysts in various types of (asymmetric) organic reactions; important contributions will be summarized. Utilization of photoactive terpyridine complexes in energy-transfer reactions will be considered with respect to “artificial photosynthesis” and photocatalytic water splitting reactions.

Finally, Chapter 10 provides a few concluding remarks.

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