Poly(cyclosilane) Connectivity Tunes Optical Absorbance

Fang, Fan; Jiang, Qifeng; Klausen, Rebekka S.

doi:10.1021/jacs.2c01820

Poly(cyclosilane) Connectivity Tunes Optical Absorbance

Journal Article · Mon Apr 25 00:00:00 EDT 2022 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c01820· OSTI ID:1864628

Fang, Fan ^[1]; Jiang, Qifeng ^[2]; ^[2]

Johns Hopkins Univ., Baltimore, MD (United States); Johns Hopkins University
Johns Hopkins Univ., Baltimore, MD (United States)

We report herein the influence of skeletal connectivity on the conformation-dependent optical properties of cyclosilane homo- and copolymers. 1,3-Linked cyclosilanes were bathochromically shifted by 20 nm in solution relative to 1,4-linked cyclosilanes, an effect reproduced by quantum chemical calculations on oligomeric model systems. Polysilane optical properties are conformation-dependent, and 1,3-linked cyclosilanes were hypothesized to adopt a favorable conformation unavailable to 1,4-linked cyclosilanes constrained to an endocyclic gauche conformation. Copolymerization of the isomeric cyclosilanes 1,3Si₆ and 1,4Si₆ afforded linear statistical copolymers, as characterized by ¹H and ²⁹Si NMR spectroscopies. The distinct connectivity of each comonomer was found to give rise to tunable absorption spectra, where the position of the absorption band systematically increased with the increased corporation of 1,3Si₆. Computational studies pointed to conformation-dependent changes in orbital symmetry in shifting the most intense transition from the low-energy highest occupied molecular orbital (HOMO) → lowest unoccupied molecular orbital (LUMO) transition to a higher-energy HOMO → LUMO + n transition. Here, the results of these studies demonstrate for the first time the role of silicon skeletal connectivity in controlling conformation and optoelectronic properties and provide new insight into the structure-based design of solution-processable silicon-based polymeric materials.

View Accepted Manuscript (DOE)

Research Organization:: Johns Hopkins Univ., Baltimore, MD (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0020681

OSTI ID:: 1864628

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 17 Vol. 144; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (49)

Conformation Control of Oligosilanes Based on Configurationally Constrained Bicyclic Disilane Units Tamao, Kohei; Tsuji, Hayato; Terada, Masayoshi Angewandte Chemie, Vol. 39, Issue 18 https://doi.org/10.1002/1521-3773(20000915)39:18<3287::AID-ANIE3287>3.0.CO;2-Q	journal	September 2000
Synthesis of a Fragment of Crystalline Silicon: Poly(Cyclosilane) Press, Eric M.; Marro, Eric A.; Surampudi, Sravan K. Angewandte Chemie International Edition, Vol. 56, Issue 2 https://doi.org/10.1002/anie.201610208	journal	November 2016
A BN Aromatic Ring Strategy for Tunable Hydroxy Content in Polystyrene van de Wouw, Heidi L.; Lee, Jae Young; Awuyah, Elorm C. Angewandte Chemie International Edition, Vol. 57, Issue 6 https://doi.org/10.1002/anie.201711650	journal	January 2018
Functional Polymeric Materials Based on Main-Group Elements Vidal, Fernando; Jäkle, Frieder Angewandte Chemie International Edition, Vol. 58, Issue 18 https://doi.org/10.1002/anie.201810611	journal	February 2019
Properties and applications of polysilanes Kumar, Vipin B.; Leitao, Erin M. Applied Organometallic Chemistry, Vol. 34, Issue 3 https://doi.org/10.1002/aoc.5402	journal	January 2020
Metal-Free Polymerization of Phenylsilane: Tris(pentafluorophenyl)borane-Catalyzed Synthesis of Branched Polysilanes at Elevated Temperatures Feigl, Andreas; Chiorescu, Ion; Deller, Katrin Chemistry - A European Journal, Vol. 19, Issue 37 https://doi.org/10.1002/chem.201203139	journal	July 2013
Chair, Boat and Twist Conformation of Dodecamethylcyclohexasilane and Undecamethylcyclohexasilane: A Combined DFT and Raman Spectroscopic Study Tekautz, Günter; Binter, Alexandra; Hassler, Karl ChemPhysChem, Vol. 7, Issue 2 https://doi.org/10.1002/cphc.200500417	journal	January 2006
Electronic Transitions in Conformationally Controlled Peralkylated Hexasilanes Kanazawa, Yuki; Tsuji, Hayato; Ehara, Masahiro ChemPhysChem, Vol. 17, Issue 19 https://doi.org/10.1002/cphc.201600633	journal	August 2016
29Si nuclear magnetic resonance of dimethyl and phenylmethyl containing polysilanes Wolff, Andrew R.; Nozue, Ikuo; Maxka, Jim Journal of Polymer Science Part A: Polymer Chemistry, Vol. 26, Issue 3 https://doi.org/10.1002/pola.1988.080260303	journal	March 1988
Condensation of primary silanes in the presence of Cp2MCl2/nBuLi (M  Ti, Zr, Hf) Corey, Joyce Y.; Xiao-Hong, Zhu Journal of Organometallic Chemistry, Vol. 439, Issue 1 https://doi.org/10.1016/0022-328X(92)80048-3	journal	October 1992
Dehydrierende copolymerisation zu den neuen polysilan-copolymeren poly(methyl-co-phenylsilan) H[(MeSiH)x(PhSiH)y]nH und Poly(methyl-co-dimethylsilan) H[(MeSiH)x(Me2S)y]nH Hengge, E.; Weinberger, M. Journal of Organometallic Chemistry, Vol. 441, Issue 3 https://doi.org/10.1016/0022-328X(92)80171-S	journal	December 1992
Ultraviolet properties of compounds containing the silicon-silicon bond Gilman, Henry; Atwell, William H.; Schwebke, Gerald L. Journal of Organometallic Chemistry, Vol. 2, Issue 4 https://doi.org/10.1016/S0022-328X(00)82225-1	journal	October 1964
Conformational studies by dynamic NMR. 66. Ring inversion in a cyclic disilane: 1,1,4,4-tetramethyl-1,4-disilacyclohexane Casarini, Daniele; Lunazzi, Lodovico; Mazzanti, Andrea Tetrahedron, Vol. 54, Issue 43 https://doi.org/10.1016/S0040-4020(98)00799-6	journal	October 1998
Silane and Germane Molecular Electronics Su, Timothy A.; Li, Haixing; Klausen, Rebekka S. Accounts of Chemical Research, Vol. 50, Issue 4 https://doi.org/10.1021/acs.accounts.7b00059	journal	February 2017
Conjugated Polymers Inspired by Crystalline Silicon Marro, Eric A.; Klausen, Rebekka S. Chemistry of Materials, Vol. 31, Issue 7 https://doi.org/10.1021/acs.chemmater.9b00131	journal	March 2019
Investigating the Microstructure of Poly(cyclosilane) by 29 Si Solid-State NMR Spectroscopy and DFT Calculations Dorn, Rick W.; Marro, Eric A.; Hanrahan, Michael P. Chemistry of Materials, Vol. 31, Issue 21 https://doi.org/10.1021/acs.chemmater.9b03606	journal	October 2019
Softwood Lignin-Based Methacrylate Polymers with Tunable Thermal and Viscoelastic Properties Holmberg, Angela L.; Nguyen, Ngoc A.; Karavolias, Michael G. Macromolecules, Vol. 49, Issue 4 https://doi.org/10.1021/acs.macromol.5b02316	journal	February 2016
Conformations of Linear Chains. Systematics and Suggestions for Nomenclature Michl, Josef; West, Robert Accounts of Chemical Research, Vol. 33, Issue 12 https://doi.org/10.1021/ar0001057	journal	December 2000
The coordination polymerization of silanes to polysilanes by a ".sigma.-bond metathesis" mechanism. Implications for linear chain growth Tilley, T. Don Accounts of Chemical Research, Vol. 26, Issue 1 https://doi.org/10.1021/ar00025a004	journal	January 1993
Polysilane high polymers Miller, Robert D.; Michl, Josef Chemical Reviews, Vol. 89, Issue 6 https://doi.org/10.1021/cr00096a006	journal	September 1989
Thermomechanical and Rheological Studies of Copolymers of Methyl Methacrylate with a Series of Linear Vinyl Esters Wang, Hai; Kolodka, Edward; Tande, Brian M. Industrial & Engineering Chemistry Research, Vol. 52, Issue 14 https://doi.org/10.1021/ie400090t	journal	March 2013
Anomalously long-wavelength electronic transition in conformationally locked organosilane high polymers Miller, Robert D.; Hofer, D.; Rabolt, J. Journal of the American Chemical Society, Vol. 107, Issue 7 https://doi.org/10.1021/ja00293a058	journal	April 1985
Phenylmethylpolysilanes: formable silane copolymers with potential semiconducting properties West, Robert; David, Lawrence D.; Djurovich, Peter I. Journal of the American Chemical Society, Vol. 103, Issue 24 https://doi.org/10.1021/ja00414a061	journal	December 1981
Polydimethylsilanes Burkhard, Charles A. Journal of the American Chemical Society, Vol. 71, Issue 3 https://doi.org/10.1021/ja01171a055	journal	March 1949
σσ* Transition in anti,cisoid Alternating Oligosilanes: Clear-Cut Evidence for Suppression of Conjugation Effect by a cisoid Turn Tsuji, Hayato; Terada, Masayoshi; Toshimitsu, Akio Journal of the American Chemical Society, Vol. 125, Issue 25 https://doi.org/10.1021/ja034500e	journal	June 2003
a ll-anti -Octasilane: Conformation Control of Silicon Chains Using the Bicyclic Trisilane as a Building Block Fukazawa, Aiko; Tsuji, Hayato; Tamao, Kohei Journal of the American Chemical Society, Vol. 128, Issue 21 https://doi.org/10.1021/ja0616231	journal	May 2006
Increasing Molecular Weight Parameters of a Helical Polymer through Polymerization in a Chiral Solvent Holder, Simon J.; Achilleos, Mariliz; Jones, Richard G. Journal of the American Chemical Society, Vol. 128, Issue 38 https://doi.org/10.1021/ja064587e	journal	September 2006
Conductive Molecular Silicon Klausen, Rebekka S.; Widawsky, Jonathan R.; Steigerwald, Michael L. Journal of the American Chemical Society, Vol. 134, Issue 10 https://doi.org/10.1021/ja211677q	journal	March 2012
Directional Building Blocks Determine Linear and Cyclic Silicon Architectures Marro, Eric A.; Press, Eric M.; Siegler, Maxime A. Journal of the American Chemical Society, Vol. 140, Issue 18 https://doi.org/10.1021/jacs.8b02541	journal	April 2018
Understanding the Effect of Conformation on Hole Delocalization in Poly(dimethylsilane) Jovanovic, Milena; Michl, Josef Journal of the American Chemical Society, Vol. 140, Issue 36 https://doi.org/10.1021/jacs.8b05829	journal	August 2018
Effect of Conformation on Electron Localization and Delocalization in Infinite Helical Chains [X(CH ₃ ) ₂ ] _∞ (X = Si, Ge, Sn, and Pb) Jovanovic, Milena; Michl, Josef Journal of the American Chemical Society, Vol. 141, Issue 33 https://doi.org/10.1021/jacs.9b04780	journal	July 2019
Conformational Studies by Dynamic NMR. 67. ¹ Ring Inversion, in Solution and in the Solid, of the Silane Analogue of Permethylcyclohexane: Dodecamethylcyclohexasilane Casarini, Daniele; Lunazzi, Lodovico; Mazzanti, Andrea The Journal of Organic Chemistry, Vol. 63, Issue 24 https://doi.org/10.1021/jo9814400	journal	November 1998
Studies of chain conformational kinetics in poly(di-n-alkylsilanes) by spectroscopic methods. 1. Poly(di-n-hexylsilane), poly(di-n-heptylsilane), and poly(di-n-octylsilane) Rabolt, J. F.; Hofer, D.; Miller, R. D. Macromolecules, Vol. 19, Issue 3 https://doi.org/10.1021/ma00157a021	journal	May 1986
Multihydroxy-Functional Polysilanes via an Acetal Protecting Group Strategy Reuss, Valerie S.; Frey, Holger Macromolecules, Vol. 43, Issue 20 https://doi.org/10.1021/ma1016715	journal	September 2010
Multiblock Polysilane Copolymers: One-Pot Wurtz Synthesis, Fluoride Anion-Induced Block-Selective Scission Experiments, and Spectroscopic Characterization Kawabe, Takuma; Naito, Masanobu; Fujiki, Michiya Macromolecules, Vol. 41, Issue 6 https://doi.org/10.1021/ma702639f	journal	February 2008
Reappraisal of the Origins of the Polymodal Molecular Mass Distributions in the Formation of Poly(methylphenylsilylene) by the Wurtz Reductive-Coupling Reaction Jones, Richard G.; Budnik, Ulrich; Holder, Simon J. Macromolecules, Vol. 29, Issue 25 https://doi.org/10.1021/ma960496y	journal	January 1996
Dehydrogenative coupling of substituted phenylsilanes: synthesis of poly[((trifluoromethyl)phenyl)silanes] Banovetz, John P.; Suzuki, Hiroshi; Waymouth, Robert M. Organometallics, Vol. 12, Issue 11 https://doi.org/10.1021/om00035a070	journal	November 1993
Catalytic dehydrogenative coupling of secondary silanes with Cp2MCl2-BuLi Corey, Joyce Y.; Zhu, Xiao Hong.; Bedard, Thomas C. Organometallics, Vol. 10, Issue 4 https://doi.org/10.1021/om00050a024	journal	April 1991
Dehydrogenative coupling of diarylsilanes Chang, Lihsueh S.; Corey, Joyce Y. Organometallics, Vol. 8, Issue 8 https://doi.org/10.1021/om00110a010	journal	August 1989
Organosilane high polymers: thermochromic behavior in solution Trefonas, Peter.; Damewood, James R.; West, Robert. Organometallics, Vol. 4, Issue 7 https://doi.org/10.1021/om00126a038	journal	July 1985
Stereoelectronic switching in single-molecule junctions Su, Timothy A.; Li, Haixing; Steigerwald, Michael L. Nature Chemistry, Vol. 7, Issue 3 https://doi.org/10.1038/nchem.2180	journal	February 2015
Comprehensive suppression of single-molecule conductance using destructive σ-interference Garner, Marc H.; Li, Haixing; Chen, Yan Nature, Vol. 558, Issue 7710 https://doi.org/10.1038/s41586-018-0197-9	journal	June 2018
Polymers and the p-block elements Priegert, Andrew M.; Rawe, Benjamin W.; Serin, Spencer C. Chemical Society Reviews, Vol. 45, Issue 4 https://doi.org/10.1039/C5CS00725A	journal	January 2016
Conformations of cyclopentasilane stereoisomers control molecular junction conductance Li, Haixing; Garner, Marc H.; Shangguan, Zhichun Chemical Science, Vol. 7, Issue 9 https://doi.org/10.1039/C6SC01360K	journal	January 2016
Metallocene influence on poly(cyclosilane) structure and properties Folster, Carlton P.; Klausen, Rebekka S. Polymer Chemistry, Vol. 9, Issue 15 https://doi.org/10.1039/C8PY00312B	journal	January 2018
Long-range coupling in cyclic silanes Ferguson, John T.; Jiang, Qifeng; Marro, Eric A. Dalton Transactions, Vol. 49, Issue 42 https://doi.org/10.1039/D0DT03163A	journal	January 2020
Effect of polycyclosilane microstructure on thermal properties Jiang, Qifeng; Wong, Sydnee; Klausen, Rebekka S. Polymer Chemistry, Vol. 12, Issue 33 https://doi.org/10.1039/D1PY00383F	journal	January 2021
Random heteropolymers preserve protein function in foreign environments Panganiban, Brian; Qiao, Baofu; Jiang, Tao Science, Vol. 359, Issue 6381 https://doi.org/10.1126/science.aao0335	journal	March 2018
Chemoselectivity in the Dehydrocoupling Synthesis of Higher Molecular Weight Polysilanes Lunzer, Florian; Marschner, Christoph Materials, Vol. 3, Issue 2 https://doi.org/10.3390/ma3021125	journal	February 2010

Similar Records

Conjugation in Isomeric Cyclosilane Thioethers

Journal Article · Tue Nov 29 19:00:00 EST 2022 · Organometallics · OSTI ID:1900518

Effect of polycyclosilane microstructure on thermal properties

Journal Article · Thu Apr 29 20:00:00 EDT 2021 · Polymer Chemistry · OSTI ID:1780587

Investigating the Microstructure of Poly(cyclosilane) by ²⁹Si Solid-State NMR Spectroscopy and DFT Calculations

Journal Article · Sun Oct 13 20:00:00 EDT 2019 · Chemistry of Materials · OSTI ID:1570241

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Absorption
Conformation
Copolymerization
Copolymers
Homopolymers

Poly(cyclosilane) Connectivity Tunes Optical Absorbance

Citation Formats

References (49)

Similar Records

Related Subjects