Novel Nanoscale Hybrid Materials E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 621

Veröffentlichungsjahr: 2018

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A comprehensive resource filled with strategic insights, tools, and techniques for the design and construction of hybrid materials Hybrid materials represent the best of material properties being combined for the development for materials with properties otherwise unavailable for application requirements. Novel Nanoscale Hybrid Materials is a comprehensive resource that contains contributions from a wide range of noted scientists from various fields, working on the hybridization of nanomolecules in order to generate new materials with superior properties. The book focuses on the new directions and developments in design and application of new materials, incorporating organic/inorganic polymers, biopolymers, and nanoarchitecture approaches. This book delves deeply into the complexities that arise when characteristics of a molecule change on the nanoscale, overriding the properties of the individual nanomolecules and generating new properties and capabilities altogether. The main topics cover hybrids of carbon nanotubes and metal nanoparticles, semiconductor polymer/biopolymer hybrids, metal biopolymer hybrids, bioorganic/inorganic hybrids, and much more. This important resource: * Addresses a cutting-edge field within nanomaterials by presenting a groundbreaking topics that address hybrid nanostructures * Includes contributions from an interdisciplinary group of chemists, physicists, materials scientists, chemical and biomedical engineers * Contains applications in a wide-range of fields--including biomedicine, energy, catalysis, green chemistry, graphene chemistry, and environmental science * Offers expert commentaries that explore potential future avenues of future research trends Novel Nanoscale Hybrid Materials is an important resource for chemists, physicists, materials, chemical and biomedical engineers that offers the most recent developments and techniques in hybrid nanostructures.

Leseprobe

Novel Nanoscale Hybrid Materials

Edited by

Bhanu P. S. Chauhan

Department of ChemistryWilliam Paterson UniversityWayne, NJ, USA

This edition first published 2018© 2018 John Wiley & Sons, Inc.

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Names: Chauhan, Bhanu P. S., editor.Title: Novel nanoscale hybrid materials / edited by Bhanu P. S. Chauhan.Description: Hoboken, NJ : John Wiley & Sons, 2018. | Includes bibliographical references and index. |Identifiers: LCCN 2017036464 (print) | LCCN 2017046280 (ebook) | ISBN 9781119156277 (pdf) | ISBN 9781119156260 (epub) | ISBN 9781119156246 (cloth)Subjects: LCSH: Nanostructured materials. | Composite materials.Classification: LCC TA418.9.N35 (ebook) | LCC TA418.9.N35 N675 2018 (print) | DDC 620.1/18–dc23LC record available at https://lccn.loc.gov/2017036464

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Om Shree Guruve Namah

to my life lines bholu, doujal, and shatiandto my big brother a hero of all heros in my life

List of Contributors

A. BagasaoDepartment of ChemistryHoward UniversityWashington, DCUSA

K. CassimereDepartment of ChemistryHoward UniversityWashington, DCUSA

Jun ChenChemistry DepartmentUniversity of Alabama at BirminghamBirmingham, ALUSA

Michèle ChevrierInstitut Charles Gerhardt – UMR 5253Université de Montpellier CNRS ENSCM – CC1701MontpellierFrance

and

Laboratory of Polymeric and Composite MaterialsCenter of Innovation and Research in Materials and Polymers, University of Mons – UMONSMonsBelgium

Sébastien ClémentInstitut Charles Gerhardt – UMR 5253Université de Montpellier CNRS ENSCM – CC1701MontpellierFrance

Olivier CoulembierLaboratory of Polymeric and Composite MaterialsCenter of Innovation and Research in Materials and Polymers, University of Mons – UMONSMonsBelgium

Jessica CzarneckiDepartment of ChemistryWilliam Paterson UniversityWayne, NJUSA

Debarshi DasguptaGlobal Research & Development Centre, India Technology CentreMomentive Performance Materials Pvt. LtdBangaloreIndia

Riccardo Di CiuccioLaboratory of Polymeric and Composite MaterialsCenter of Innovation and Research in Materials and Polymers, University of Mons – UMONSMonsBelgium

Philippe DuboisLaboratory of Polymeric and Composite MaterialsCenter of Innovation and Research in Materials and Polymers, University of Mons – UMONSMonsBelgium

Noor EldabaghDepartment of ChemistryWilliam Paterson UniversityWayne, NJUSA

Hisayuki EndoDepartment of Chemistry and Chemical Biology, Graduate School of Science and TechnologyGunma UniversityKiryuJapan

Jonathan J. Foley IVDepartment of ChemistryWilliam Paterson UniversityWayne, NJUSA

Fatima Abi GhaidaInstitut Charles Gerhardt – UMR 5253Université de Montpellier CNRS ENSCM – CC1701MontpellierFrance

and

Faculty of Sciences I, Inorganic and Organometallic Coordination Chemistry Laboratory (LCIO)Lebanese UniversityHadathLebanon

Tijana Z. GroveDepartment of ChemistryVirginia Polytechnic Institute and State UniversityBlacksburg, VAUSA

K. HollowayDepartment of ChemistryHoward UniversityWashington, DCUSA

A. KarimDepartment of Chemical and Biomolecular EngineeringUniversity of HoustonHouston, TXUSA

Eugenia KharlampievaChemistry DepartmentUniversity of Alabama at BirminghamBirmingham, ALUSA

Veronika KozlovskayaChemistry DepartmentUniversity of Alabama at BirminghamBirmingham, ALUSA

Prajakta KulkarniDepartment of Pharmaceutical SciencesNorth Dakota State UniversityFargo, NDUSA

Sanku MallikDepartment of Pharmaceutical SciencesNorth Dakota State UniversityFargo, NDUSA

Ahmad MehdiInstitut Charles Gerhardt – UMR 5253Université de Montpellier CNRS ENSCM – CC1701MontpellierFrance

Daniëlle PretoriusChemistry DepartmentUniversity of Alabama at BirminghamBirmingham, ALUSA

D. RaghavanDepartment of ChemistryHoward UniversityWashington, DCUSA

Sébastien RicheterInstitut Charles Gerhardt – UMR 5253Université de Montpellier CNRS ENSCM – CC1701MontpellierFrance

Kristina L. RothDepartment of ChemistryVirginia Polytechnic Institute and State UniversityBlacksburg, VAUSAandDepartment of ChemistryRadford UniversityRadford, VAUSA

Alok SarkarGlobal Research & Development Centre, India Technology CentreMomentive Performance Materials Pvt. LtdBangaloreIndia

Anubhav SaxenaGlobal Research & Development Centre, India Technology CentreMomentive Performance Materials Pvt. LtdBangaloreIndia

Masafumi UnnoDepartment of Chemistry and Chemical Biology, Graduate School of Science and TechnologyGunma UniversityKiryuJapan

Marc A. WaltersDepartment of ChemistryNew York UniversityNew York, NYUSA

Dieter WrobelResearch & Development CentreMomentive Performance Materials GmbHLeverkusenGermany

B. ZewdeDepartment of ChemistryHoward UniversityWashington, DCUSA

I. J. ZvonkinaDepartment of Chemical and Biomolecular Engineering,University of HoustonHouston, TXUSA

1Silanols as Building Blocks for Nanomaterials

Masafumi Unno and Hisayuki Endo

Department of Chemistry and Chemical Biology, Graduate School of Science and Technology, Gunma University, Kiryu, Japan

1.1 Introduction

Silanols have been recognized as reactive intermediates and easily condense to form siloxanes. Therefore, most of the early research on the synthesis and isolation of organosilanols utilized an introduction of bulky substituents. The condensation of silanols is accelerated by an existence of acid or base; therefore preparation from chlorosilanes or alkoxysilanes often encountered further condensation reactions. However, when several important factors (acid, base, concentration, temperature) were carefully considered in the reactions, isolation of organosilanols even with smaller substituents was possible, and many isolated silanols have been shown to be stable in the air. Recently accumulating results have been recorded on the isolation of silanols [1, 2].

Silanols are silicon analogue of alcohols; however, in addition to the monosilanols (R3SiOH), silanediols and silanetriols (R2Si(OH)2 and RSi(OH)3) are also isolable. Because hydroxyl groups play an important role in interactions of molecules or biological species, silanols with multiple hydroxyl groups (often quoted as polysilanols) were expected to serve as useful components of hydrogen‐bonded supramolecular aggregates [3, 4] or host molecules [5]. In addition, polysilanols are also potential precursors of siloxanes or silsesquioxanes with well‐defined structures [6–10] because various bonding schemes are possible. Detailed chemistry of polysilanols can be found in reviews [11–13].

Most of silicone materials have been produced by controlled hydrolysis/condensation from monosilanes like halosilanes or alkoxysilanes. However, this method affords only kinetically or thermodynamically most stable compounds, and usually well‐defined nanomaterials could not be obtained. In order to construct defined structure of siloxanes, coupling reactions from two different compounds (cross‐coupling reaction) are necessary. The reaction from chlorosilanes and silanols in the existence of organic base to form siloxane [8, 9] has been mostly utilized. More recently catalytic siloxane formation from hydrosilanes and silanols/alkoxysilanes was developed [14, 15] and has been widely employed for nanomaterial synthesis. As clearly seen in these examples, silanols are most potential precursors of well‐defined siloxanes.

In this chapter, our results in the last two decades regarding synthesis and structure identification of silanols and their application to the precursors of nanomaterials are summarized.

1.2 Synthesis and Applications of Silanols

1.2.1 Silanetriols and Disiloxanetetraols

Our first encounter with polysilanols was in the process of synthesis of cage silsesquioxanes [6]. Although cage octasilsesquioxanes have been prepared easily from trichlorosilanes or trialkoxysilanes, small cages, for example, hexasilsesquioxanes, were hard to obtain [16]. In order to obtain smaller cages, we introduced bulky groups to stabilize strained cage framework. According to the typical synthetic method for cage silsesquioxane, we examined the hydrolytic condensation from t‐BuSiCl3 or ThexSiCl3 (Thex = 1,1,2‐trimethylpropyl) to obtain cage hexasilsesquioxanes. Against expectation, obtained white solid was not the targeted hexasilsesquioxanes but silanetriols (t‐BuSi(OH)3 and ThexSi(OH)3). Interestingly, both compounds are air‐stable white solid and can be stored without problems. We then traced back the literatures and optimized the reaction condition (Scheme 1.1). Synthesis of t‐BuSi(OH)3 was effected by following the method by Roesky’s group [17]; thus t‐BuSiCl3was treated with aniline/water in ether, and target compound was obtained. For ThexSi(OH)3, we applied Takiguchi’s method [18] and silanetriols were obtained in 64% yield from ThexSiCl3.

Scheme 1.1 Preparation of silanetriols and disiloxanetetraols.

Similarly, disiloxanetetraols were also obtained from trichlorosilanes. By following the Sommer and Tyler’s method [19], reaction of ThexSiCl3 with KOH, silica gel, and water in ethanol afforded 1,3‐bis(1,1,2‐trimethylpropyl)‐1,1,3,3‐tetrahydroxydisiloxane in 47% yield. Disiloxanetetraol with tert‐butyl groups was obtained from t‐BuSiCl3 by the reported method by Lickiss et al. [20].

With four silanols in hand, we then tried the synthesis of silsesquioxanes from silanols. At that time, many silanols were isolated and structures were determined; however, reactions starting from silanols were not known. In order to stabilize silanols against dehydration, most of isolated silanols possess bulky substituents, and their reactivity was low. We determined to use dicyclohexylcarbodiimide (DCC) as dehydrating reagent, and after several examinations of reaction conditions, we found that reactions at higher temperature in polar solvent afforded the target compounds. Thus treating silanetriols or disiloxanetetraols with DCC in dimethyl sulfoxide (DMSO) or DMF at 120°C, cage hexasilsesquioxanes were obtained in 25–41% yields (Scheme 1.2). We carefully examined the reaction mixture, but no other cage silsesquioxanes (T8 or T10) were not obtained. The structure of hexasilsesquioxane was established unequivocally by X‐ray crystallographic analysis. Prior to our work, synthesis of cyclohexyl‐substituted hexasilsesquioxane was reported by the reaction from cyclohexyltrichlorosilane in acetone/water for 4 months [21, 22]. Our method offered more facile access to hexasilsesquioxanes.

Scheme 1.2 Synthesis of hexasilsesquioxanes from silanols.

Later we applied this reaction to other silanols and obtained several cage silsesquioxanes (Scheme 1.3). Cage hexasilsesquioxanes with bulky mesityl (Unno, M., Imai, Y., Matsumoto, H., unpublished result) or Tip (triisopropylphenyl) groups [10] were obtained from respecting silanols by the reactions with DCC. In the case of mesityl‐substituted silanols, both hexasilsesquioxane (6%) and octasilsesquioxane (20%) were obtained (Unno, M., Imai, Y., Matsumoto, H., unpublished result). Similar reaction starting from dicyclohexyldisiloxanetetraol afforded octasilsesquioxane in 13% yield [7].

Scheme 1.3 Synthesis of hexasilsesquioxanes from silanols.

It should be noted that hexasilsesquioxane with the most bulky Tip group showed interesting structure [10]. With bulky triisopropylphenyl groups, six Tip groups can only rotate with gear‐like motion. In the single crystal, a pair of enantiomer exists and Tip groups are twisted like three blades of a propeller (Figure 1.1). In solution, gear‐like rotation could be observed by 1H NMR; two different singlet peaks are observed for aryl protons at low temperature (exo‐proton: outer of the cage; endo‐proton: inner of the cage (see Figure 1.1)), and Tip groups start rotating by elevating temperature. The coalescence temperature was 38°C, and above this temperature, Tip groups freely rotate to show only single acrylic proton. The activation free energy (ΔG‡) was calculated to be 14.8 kcal mol−1.

Figure 1.1 Side view of the crystal structure and two inequivalent acrylic protons of Tip‐T6.

As shown in these results, hexasilsesquioxanes with relatively smaller substituents were hard to be obtained because octasilsesquioxanes generate preferably. We applied a reaction from cyclic silanols (details are described in the following section), and reaction with tetrachlorodisiloxane afforded isopropyl‐substituted hexasilsesquioxane [8]. This is the hexasilsesquioxane ever known with the smallest substituents (Scheme 1.4). Cage octasilsesquioxane was also obtained from cyclic silanols [8].

Scheme 1.4 Synthesis of cage silsesquioxanes from cyclic silanols.

Octasilsesquioxanes could also be prepared from disiloxanetetraol. From cyclohexyl disiloxanetetraol, reaction with DCC in DMSO at 120°C afforded octasilsesquioxane in 13% yield (Scheme 1.5) [7]. When cyclohexyltrichlorosilane was hydrolyzed and condensed in acetone/water, hexasilsesquioxane was obtained as reported [21]. More recently Bassindale and Taylor’s group reported the synthesis of cage silsesquioxanes by nonaqueous hydrolysis of trichlorosilanes with DMSO [23]. In our case starting from silanol, high reaction temperature favored the generation of more thermodynamically stable T8 cage.

Scheme 1.5 Synthesis of octasilsesquioxanes from disiloxanetetraol.

1.2.2 Cyclotetrasiloxanetetraol (Cyclic Silanols, All‐cis Isomer)

At the same time we investigated cage silsesquioxanes, we were also interested in ladder silsesquioxanes. Although the structure was proposed in 1960 [24] and various superior properties were expected, obtaining well‐defined ladder silsesquioxanes is still challenging. Our first trial to obtain ladder silsesquioxanes was targeting bicyclic ones, and we treated tetrachlorodisiloxane with disiloxanetetraol. The reaction is simple dehydrochlorination reaction, and we succeed to obtain a mixture of stereoisomers with expected molecular weight. We isolated all isomers by recycle‐type HPLC, and the structures were determined by X‐ray crystallographic analysis. To our surprise, obtained compound was not bicyclic ladder silsesquioxanes but a stereoisomer containing two six‐membered rings (Scheme 1.6) (Unno, M.; Suto, A.; Matsumoto, H., unpublished result).

Scheme 1.6 Attempted synthesis of bicyclic laddersiloxane.

With this result, we realized that fused eight‐membered ring ladder silsesquioxanes could only be obtained from the precursors containing cyclotetrasiloxane rings. Then we set the target compound to be the cyclotetrasiloxanes with reactive substituents. As we already knew that silanols were stabilized with even relatively smaller substituents, we chose isopropyl groups as substituents. As shown in Scheme 1.7, we first applied the stepwise synthesis [4]. After obtaining the target compound, we also succeeded to prepare the compound directly from isopropyltrichlorosilane [8].

Scheme 1.7 Synthesis of cyclic silanols.

The key step of laddersiloxane synthesis is substitution reaction of phenyl groups into chlorine atoms. Aluminum chloride has been known to cleave Si–O bonds [25], so this dephenylchlorination was not applied to siloxanes. However, if substituent on silicon atom is larger than methyl, replacement reaction occurs in quantitative yield. This reaction is also an important step to obtain well‐defined laddersiloxanes [9].

Cyclic silanols with the similar structure were previously reported, and substituents were phenyl [26] and cyclohexyl [21] groups. However, there was no evidence for the all‐cis conformation. Out of four possible stereoisomers (Scheme 1.8), cis,cis,trans‐isomer can be identified with NMR spectra because three independent silicon atoms and substituents exist. On the other hand, identification of other three isomers is impossible from spectroscopic analysis. In order to construct ladder structures, stereostructure of the starting compound is very important; therefore we tried to obtain a single crystal to determine the structure. Unfortunately, crystallinity of obtained isopropyl cyclic silanol was not good, and no suitable crystals were obtained after several months of trials. Finally a single crystal generated from the solvent containing water, and the result clearly indicated the structure was all‐cis [4]. Almost at the same time, Feher’s group succeeded to determine the structure of phenyl‐substituted cyclic silanol [27]. We also reported the crystallographic analysis of supramolecular aggregates of this cyclic silanol with i‐Pr2Si(OH)2 [3].

Scheme 1.8 Four stereoisomers of cyclotetrasiloxanetetraols.

As expected, obtained cyclic silanol served as a quite potential starting material for well‐defined siloxanes. For example, perfect ladder silsesquioxanes (we termed “laddersiloxane” for those whose structure was unequivocally determined) up to nonacyclic could be obtained starting from cyclic silanols. As an example, synthesis of pentacyclic laddersiloxane is shown in Scheme 1.9 [9].

Scheme 1.9 Synthesis of pentacyclic laddersiloxane.

This synthesis was based on the coupling reaction of silanols with chlorosilanes. We investigated several combinations of base and solvent and found out that using pyridine as solvent afforded highest yield. As mentioned in the previous section, exchange reaction of phenyl groups into chlorine atoms is also a key step of this synthesis. Obtained laddersiloxanes were mixture of isomers because of the orientation of terminal isopropyl and phenyl groups; however, the stereostructure of starting cyclic silanol (all‐cis) was perfectly maintained throughout the synthesis, and no stereoisomerization of siloxane framework was observed. The structure of pentacyclic laddersiloxane was determined by X‐ray crystallography [9].

Syntheses of well‐defined siloxanes starting from all‐cis cyclic silanol are summarized in Scheme 1.10. Not only laddersiloxanes, cage silsesquioxanes, or metallasiloxanes [28] (obtained from cyclic silanols and (CpTiCl2)2O) could also be accessed from this single starting compound, showing its versatility. In the synthesis of longer laddersiloxane, we developed a stereocontrolled approach by use of single diastereomer [29]. Chemistry of laddersiloxanes is summarized in a recent review [30].

Scheme 1.10 Well‐defined siloxanes prepared from cyclic silanols.

Even though the stepwise synthesis afforded the highly ordered laddersiloxanes, preparation of ladder polysilsesquioxanes is still a challenging topic. Condensation of cyclic silanols seems to offer an effective pathway to ladder polysilsesquioxanes; however, cyclic silanols are basically stable and no condensation is observed in neutral condition. Kawakami’s group reported that phenyl cyclic silanols showed stereoisomerization by an action of acid [31]. In the existence of base, siloxane bond cleavage may occur and random structure is possibly obtained. We developed the neutral dehydration reaction using DCC, but only cage silsesquioxanes were obtained from all‐cis cyclic silanols (Scheme 1.4). Therefore, currently possible pathway to perfect ladder polysilsesquioxane can be (a) cross‐coupling reactions of cyclic silanols with other substituted cyclotetrasiloxanes in a condition to avoid stereoisomerization or (b) self‐condensation of cyclic silanols other than all‐cis structure (e.g., cis,trans,cis‐isomer). In Scheme 1.11, our approach to ladder polysilsesquioxanes using cis,trans,cis‐tetrabromocyclotetrasiloxane is depicted. Starting from readily available methylphenyldichlorosilane, dehydration/condensation in THF/water afforded a mixture of 6‐, 8‐, and 10‐membered cyclic siloxanes with various stereostructures. Surprisingly, targeted cis,trans,cis‐cyclotetrasiloxane could be obtained as white solid by direct recrystallization of the mixture. Treatment of cyclotetrasiloxane with bromine afforded tetrabromide, and the stereostructure was confirmed by transfer to tricyclic laddersiloxane. This tetrabromide was moisture sensitive, and when the compound was in the air, spontaneous hydrolysis and following condensation occurred to give white solid. Although X‐ray structure analysis was not possible, the product indicated the highly ordered structure from NMR and IR spectra and from high thermal stability [32]. Unfortunately obtained white solid was insoluble to organic solvents. Then we are now investigating the synthesis of soluble ladder polysilsesquioxanes with different substituents.

Scheme 1.11 Approach to ladder polysilsesquioxane.

Our synthesis of cyclic silanols was accomplished by treatment of chlorosilanes with water in an appropriate solvent. Then various products were possible and the yields were not satisfactory. Following our report, Shchegolikhina’s group developed a high‐yield synthesis of cyclic silanols by isolating sodium or potassium silanolate [33–35]. Metal salts of organosilanols or organosilanolates were isolated and identified by Feher et al. [36], Roesky et al. [37], or Corriu’s group [38], and the Russian group showed the first result of cyclotetrasiloxane silanolates. As shown in Scheme 1.12, phenyltrialkoxysilane was treated with aqueous NaOH in butanol. After the reaction, generated white needles were collected and then treated with hydrochloric acid. The target tetraphenylcyclotetrasiloxanetetraol was obtained in 80% yield. The structure (all‐cis) was determined by X‐ray crystallography.

Scheme 1.12 Facile synthesis of cyclic silanols.

By this method, cyclic silanols with various substituents were obtained in relatively good yield with simple procedure. We applied this synthesis to various alkoxysilanes and obtained silanolates in good yields. For example, isobutyl‐substituted cyclic silanol was obtained in 74% yield from commercially available alkoxysilane. By optimizing the condition, we improved the yield from the reported one (34%) (Scheme 1.13).

Scheme 1.13 Facile synthesis of isobutyl‐substituted cyclotetrasiloxanetetraol.

Both sodium silanolate and silanol possessed all‐cis configuration, indicating no stereoisomerization occurred. It should be noted that stereoisomerization of cyclic silanols easily occurred by an action of HCl. As shown in Scheme 1.14, all‐cis phenylcyclotetrasiloxanetetraol afforded all four isomers after treatment of 1 M HCl in acetone for 10 min at room temperature. In order to avoid stereoisomerization, reaction with aqueous HCl must be maintained at low temperature and keep the reaction time short.

Scheme 1.14 Stereoisomerization of cyclotetrasiloxanetetraol.

We then investigated the preparation of silanolates in detail in order to obtain the optimized condition. We treated commercially available phenyltrimethoxysilane with aqueous NaOH in 2‐propanol. By adjusting the concentration to 2 mol l−1, highest yield 99% was recorded after 17 h of reaction at room temperature. Obtained solid indicated single peak in 29Si NMR in D2O (−54.8 ppm), and all‐cis structure was determined by treatment with dimethylchlorosilane to give all‐cis siloxycyclotetrasiloxane, whose structure was established by X‐ray crystallography (Scheme 1.15) [39].

Scheme 1.15 Synthesis of siloxycyclotetrasiloxane.

Similar transformation could be applied to isobutyl‐ and vinyl‐substituted silanolates. As shown in Scheme 1.16, substitute dimethylsiloxycyclotetrasiloxanes were obtained by facile single‐step reaction from trimethoxysilanes. In these reactions, no purification of sodium or potassium silanolates was necessary; silylation after filtration and drying of the crude product afforded good results [39]. In the case of vinyl‐substituted compound, potassium hydroxide gave better yield. In addition, treatment of dimethylchlorosilane resulted in the stereoisomerization in the case of vinyl compounds. Therefore, triethylamine was added to the reaction mixture to avoid isomerization. In each reaction, selection of the solvents is important because solubility of these salts is different by substituents.

Scheme 1.16 Synthesis of various siloxycyclotetrasiloxane.

It is noteworthy that these extended cyclic siloxanes contain reactive vinyl or hydrosilyl groups. Therefore these compounds are potential precursors for highly ordered siloxanes or siloxane‐containing organic polymers.

In addition, oxidation of these hydrosilanes with m‐chloroperbenzoic acid (mCPBA) afforded silanols (Scheme 1.17). These silanols are also interesting in view of precursors of siloxanes as well as host molecule for anions with extended silanol arms [39]. The structures of both compounds were established by X‐ray crystallographic analysis. In the crystal, the molecules form hydrogen‐bonded dimer.

Scheme 1.17 Synthesis of cyclotetrasiloxanes with extended silanol arms.

1.2.3 Cyclotetrasiloxanetetraol (Cyclic Silanols, Other Isomers)

As shown in Scheme 1.10 and following schemes, all‐cis cyclic silanol showed its capacity as the precursors of various well‐defined siloxanes. This fact also indicates the potential of other three stereoisomers. For example, as shown in scheme 1.11, cis,trans,cis‐isomer is the most promising starting compound for ladder polysilsesquioxanes, because only this isomer is capable of generating straight‐chain polymers with unlimited molecular weight. With this point of view, we investigated the synthesis of other three isomers. When we started this project, there was a report of the isomerization of all‐cis‐[PhSiO(OH)]4 with catalytic amount of organochlorosilane (Me3SiCl, Me2SiCl2), HCl, or acetic acid [40]. However, in this case no results for isolation and identification of each isomer were shown. Even though the isomerization from all‐cis isomer is most desirable because all‐cis isomer can be obtained in high yields, separation of stereoisomer of silanols seems to be difficult. Therefore, we devised a method: (i) separation of stereoisomers of phenyl‐substituted cyclotetrasiloxane (D4), (ii) replacement of phenyl groups of each compound with chlorine atom by dearylchlorination reaction, and (iii) hydrolysis of tetrachloride to afford silanols. The key step of this synthesis is dearylchlorination step, and we have to maintain the stereostructure during this reaction. Fortunately, all reactions including hydrolysis proceeded in a stereospecific manner, and targeted isomers of cyclic silanols were all isolated. The structures were unequivocally established by X‐ray crystallography (Scheme 1.18) [41].

Scheme 1.18 Synthesis of all isomers of cyclic silanols.

Interestingly melting points of these isomers were quite different from each other (cis,trans,cis: 186–187°C, cis,cis,trans: 157–158°C, all‐trans: 160–161°C, and all‐cis: 165–169°C), reflecting the different hydrogen bonding schemes.

Although this procedure allows us to access each isomer for the first time, separation of stereoisomers with HPLC (first step) prohibited obtaining target compounds in gram quantities. More recently, the Japanese group [31] and Russian group [42] independently reported the acid‐catalyzed isomerization of phenyl‐substituted cyclic silanols. In 2014, Yagihashi and Shimada’s group reported the synthesis and isolation of stereoisomers of phenyl‐substituted cyclotrisiloxanetriols [43]. Their method could be applied to cyclotetrasiloxanetetraols to isolate stereoisomers. With these results, obtaining isomers of phenyl‐substituted cyclic silanols in larger amount is now possible; however those with alkyl or vinyl groups could not be acquired yet.

1.2.4 Cyclotrisiloxanetriol

For cyclic silanols, there is another example other than cyclotetrasiloxanetetraol, that is, cyclotrisiloxanetriols with smaller ring size (Scheme 1.19). Because six‐membered siloxane rings are more strained than eight‐membered ones, ring‐opening reactions were known. Therefore, isolation of cyclotrisiloxanetriol was limited to those with large substituents or inclusion in the inorganic cage in the early stage.

Scheme 1.19 Cyclotrisiloxanetriols.

There were several synthetic reports for [RSiO(OH)]3 (R = Ar(Me3Si)N (Ar = 2,6‐dimethylphenyl) [44], (Me3Si)2CH [45], Ph [43, 46], m‐tolyl [47], 2‐naphthyl [48], Tip (2,4,6‐triisopropylphenyl) [49], and 3,5‐xylyl [46]. Among these examples, some cyclotrisiloxanetriols were stabilized by bulky substituents: cis,trans‐[Ar(Me3Si)NSiO(OH)]3 (Ar = 2,6‐dimethylphenyl) [44] and all‐cis‐[(Me3Si)2CHSiO(OH)]3 reported by Roesky et al. and cis‐trans‐[TipSiO(OH)]3 by our group [49]. As another approach, all‐cis‐[RSiO(OH)]3 (R = Ph, m‐tolyl, 2‐naphthyl, 3,5‐xylyl) were isolated by stabilization in self‐assembled coordination cages. In many cases, cyclotrisiloxanetriols have been synthesized by multistep reaction.

In all aforementioned cases, cyclic silanols were protected by bulky substituents or included in a cage system. Therefore reactions starting from those silanols were not known. We thought, as in the case of cyclotetrasiloxanetetraols, that these cyclotrisiloxanetriols could serve as useful precursors of highly ordered siloxanes. For this point of view, we investigated the synthesis of cyclotrisiloxanetriols with relatively smaller substituents.

If hydrolytic condensation is applied to substituted trichlorosilanes or trialkoxysilanes, larger cyclotetrasiloxane rings generated with small substituents. Then we devised a new approach: dearylchlorination followed by hydrolysis. As shown in Scheme 1.20