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Third-Generation W(CNAr)₆ Photoreductants (CNAr = Fused-Ring and Alkynyl-Bridged Arylisocyanides)

Fajardo, Javier, Jr. and Schwan, Josef and Kramer, Wesley W. and Takase, Michael K. and Winkler, Jay R. and Gray, Harry B. (2021) Third-Generation W(CNAr)₆ Photoreductants (CNAr = Fused-Ring and Alkynyl-Bridged Arylisocyanides). Inorganic Chemistry, 60 (6). pp. 3481-3491. ISSN 0020-1669. doi:10.1021/acs.inorgchem.0c02912.

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Homoleptic tungsten(0) arylisocyanides possess photophysical and photochemical properties that rival those of archetypal ruthenium(II) and iridium(III) polypyridine complexes. Previous studies established that extending the π-system of 2,6-diisopropylphenylisocyanide (CNDipp) by coupling aryl substituents para to the isocyanide functionality results in W(CNDippAr)₆ oligoarylisocyanide complexes with greatly enhanced metal-to-ligand charge transfer (MLCT) excited-state properties relative to those of W(CNDipp)₆. Extending electronic modifications to delineate additional design principles for this class of photosensitizers, herein we report a series of W(CNAr)₆ compounds with naphthalene-based fused-ring (CN-1-(2-ⁱPr)-Naph) and CNDipp-based alkynyl-bridged (CNDipp^(CC)Ar) arylisocyanide ligands. Systematic variation of the secondary aromatic system in the CNDippCCAr platform provides a straightforward method to modulate the photophysical properties of W(CNDipp^(CC)Ar)₆ complexes, allowing access to an extended range of absorption/luminescence profiles and highly reducing excited states, while maintaining the high molar absorptivity MLCT absorption bands, high photoluminescence quantum yields, and long excited-state lifetimes of previous W(CNAr)₆ complexes. Notably, W(CN-1-(2-iPr)-Naph)₆ exhibits the longest excited-state lifetime of all W(CNAr)₆ complexes explored thus far, highlighting the potential benefits of utilizing fused-ring arylisocyanide ligands in the construction of tungsten(0) photoreductants.

Item Type:Article
Related URLs:
URLURL TypeDescription
Fajardo, Javier, Jr.0000-0003-0612-7953
Schwan, Josef0000-0002-1086-6698
Kramer, Wesley W.0000-0002-1359-0519
Takase, Michael K.0000-0001-8365-3645
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Alternate Title:Third-Generation W(CNAr)6 Photoreductants (CNAr = Fused-Ring and Alkynyl-Bridged Arylisocyanides)
Additional Information:© 2020 American Chemical Society. This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received 30 September 2020. Published online 6 December 2020. We thank Dr. David VanderVelde and Lawrence M. Henling for assistance with NMR and XRD experiments, respectively. The X-ray Crystallography Facility in the Beckman Institute at Caltech was supported by the Dow Next Generation Instrumentation Grant. This work was supported by the National Science Foundation (Grant CHE-1763429) and the Beckman Institute Laser Resource Center, supported by the Arnold and Mabel Beckman Foundation. Author Contributions. All authors have given approval to the final version of the manuscript. The authors declare no competing financial interest.
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Dow Next Generation Educator FundUNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
Issue or Number:6
Record Number:CaltechAUTHORS:20201208-105038243
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Official Citation:Third-Generation W(CNAr)6 Photoreductants (CNAr = Fused-Ring and Alkynyl-Bridged Arylisocyanides). Javier Fajardo, Josef Schwan, Wesley W. Kramer, Michael K. Takase, Jay R. Winkler, and Harry B. Gray. Inorganic Chemistry 2021 60 (6), 3481-3491; DOI: 10.1021/acs.inorgchem.0c02912
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:106962
Deposited By: George Porter
Deposited On:09 Dec 2020 15:20
Last Modified:26 Aug 2021 19:05

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