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Photooxidative Generation of Dodecaborate-Based Weakly Coordinating Anions

Axtell, Jonathan C. and Messina, Marco S. and Liu, Ji-Yuan and Galaktionova, Daria and Schwan, Josef and Porter, Tyler M. and Savage, Miles D. and Wixtrom, Alex I. and Rheingold, Arnold L. and Kubiak, Clifford P. and Winkler, Jay R. and Gray, Harry B. and Král, Petr and Alexandrova, Anastassia N. and Spokoyny, Alexander M. (2019) Photooxidative Generation of Dodecaborate-Based Weakly Coordinating Anions. Inorganic Chemistry, 58 (16). pp. 10516-10526. ISSN 0020-1669. doi:10.1021/acs.inorgchem.9b00935.

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Redox-active proanions of the type B_(12)(OCH_2Ar)_(12) [Ar = C_6F_5 (1), 4-CF_3C_6H_4 (2), 3,5-(CF_3)_2C_6H_3 (3)] are introduced in the context of an experimental and computational study of the visible-light-initiated polymerization of a family of styrenes. Neutral, air-stable proanions 1–3 were found to initiate styrene polymerization through single-electron oxidation under blue-light irradiation, resulting in polymers with number-average molecular weights (M_n) ranging from ∼6 to 100 kDa. Shorter polymer products were observed in the majority of experiments, except in the case of monomers containing 4-X (X = F, Cl, Br) substituents on the styrene monomer when polymerized in the presence of 1 in CH_2Cl_2. Only under these specific conditions are longer polymers (>100 kDa) observed, strongly supporting the formulation that reaction conditions significantly modulate the degree of ion pairing between the dodecaborate anion and cationic chain end. This also suggests that 1–3 behave as weakly coordinating anions (WCA) upon one-electron reduction because no incorporation of the cluster-based photoinitiators is observed in the polymeric products analyzed. Overall, this work is a conceptual realization of a single reagent that can serve as a strong photooxidant, subsequently forming a WCA.

Item Type:Article
Related URLs:
URLURL TypeDescription
Axtell, Jonathan C.0000-0002-5579-4296
Messina, Marco S.0000-0003-2827-118X
Liu, Ji-Yuan0000-0001-7905-6282
Galaktionova, Daria0000-0003-2444-7168
Schwan, Josef0000-0002-1086-6698
Porter, Tyler M.0000-0002-2693-2653
Savage, Miles D.0000-0002-6924-9360
Wixtrom, Alex I.0000-0002-0622-4633
Rheingold, Arnold L.0000-0003-4472-8127
Kubiak, Clifford P.0000-0003-2186-488X
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Alexandrova, Anastassia N.0000-0002-3003-1911
Spokoyny, Alexander M.0000-0002-5683-6240
Additional Information:© 2019 American Chemical Society. Received: March 30, 2019; Published: June 25, 2019. Special Issue: Celebrating the Year of the Periodic Table: Emerging Investigators in Inorganic Chemistry. The authors acknowledge Aayush Gupta (UIC) for preliminary computational work. M.S.M. was supported by NSF Bridge-to-Doctorate (Grant HRD-1400789) and Predoctoral Fellowship (Grant DGE-0707424) and the UCLA Christopher S. Foote Fellowship. H.B.G. was supported by the NSF (Grants CHE-1305124 and CHE-1763429). A.N.A. was supported by NSF CAREER Award CHE-1351968. Research pertaining to synthesis of the cluster compounds performed at UCLA was supported as part of the Synthetic Control Across Length-scales for Advancing Rechargeables (SCALAR) and Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award DE-SC0019381. A.M.S. thanks 3M for a Non-Tenured Faculty Award, the Alfred P. Sloan Foundation for a Fellowship in Chemistry, and the Research Corporation for Science Advancement (RCSA) for a Cottrell Scholar Award. M.D.S. acknowledges a Dr. Raymond and Dorothy Wilson Research Fellowship (UCLA). A.I.W. acknowledges the University of California, Los Angeles, Graduate Division, for a Dissertation Year Fellowship. The authors declare the following competing financial interest(s): UCLA holds patents on materials used in this work, from which A.M.S. may receive royalty payments.
Funding AgencyGrant Number
NSF Graduate Research FellowshipDGE-0707424
Department of Energy (DOE)DE-SC0019381
Alfred P. Sloan FoundationUNSPECIFIED
Cottrell Scholar of Research CorporationUNSPECIFIED
Issue or Number:16
Record Number:CaltechAUTHORS:20190625-112728745
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Official Citation:Photooxidative Generation of Dodecaborate-Based Weakly Coordinating Anions. Jonathan C. Axtell, Marco S. Messina, Ji-Yuan Liu, Daria Galaktionova, Josef Schwan, Tyler M. Porter, Miles D. Savage, Alex I. Wixtrom, Arnold L. Rheingold, Clifford P. Kubiak, Jay R. Winkler, Harry B. Gray, Petr Král, Anastassia N. Alexandrova, and Alexander M. Spokoyny. Inorganic Chemistry 2019 58 (16), 10516-10526. DOI: 10.1021/acs.inorgchem.9b00935
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:96698
Deposited By: Tony Diaz
Deposited On:25 Jun 2019 19:47
Last Modified:16 Nov 2021 17:23

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