Show simple item record

dc.contributor.authorBraun, Jason
dc.contributor.authorLozada, Issiah
dc.contributor.authorHerbert, David E
dc.date.accessioned2021-10-22T17:55:40Z
dc.date.available2021-10-22T17:55:40Z
dc.date.issued2020-11-23
dc.date.submitted2021-10-16T01:05:11Zen_US
dc.identifier.citationInorg. Chem. 2020, 59(23), 17746–17757en_US
dc.identifier.urihttp://hdl.handle.net/1993/36064
dc.description.abstractThe ability of a compound to broadly absorb light across the incident solar spectrum is an important design target in the development of molecular photosensitizers. The ‘HOMO inversion’ model predicts that for [(tpy)2Fe]2+ (tpy = 2,2′:6′,2″-terpyridine) compounds, adjusting the character of the highest occupied molecular orbital (HOMO) from metal-centered to ligand-centered can drastically improve photophysical properties by broadening absorption in the visible and increasing molar extinction coefficients. In an effort to experimentally realize strong, panchromatic absorption, a tridentate N^N–^N diarylamido ligand bearing flanking benzannulated N-heterocyclic donors (tBuL) was used to prepare deeply colored, pseudo-octahedral coordination complexes of a range of first-row transition and main-group metals [(tBuL)2M0/+; M = Fe, Co, Ni, Zn, Ga]. While the Fe(II) congener exhibits the sought-after broad absorption, isostructural and isoelectronic complexes of other first-row transition and main-group metals show vastly different absorption and redox properties. Density functional theory (DFT) calculations point toward the relative energies of the metal d orbitals and ligand orbitals as the source of major changes in electronic structure, confirming aspects and limitations of the predictive 'HOMO inversion' model in experimentally realized systems with implications for the design of abundant transition-metal sensitizers with broad, panchromatic absorptive properties.en_US
dc.description.sponsorshipNatural Sciences and Engineering Research Council of Canada (RGPIN-2014-03733)en_US
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.rightsopen accessen_US
dc.subjectCoordination Chemistryen_US
dc.titleIn Pursuit of Panchromatic Absorption in Metal Coordination Complexes: Experimental Delineation of the HOMO Inversion Model Using Pseudo-Octahedral Complexes of Diarylamido Ligandsen_US
dc.typePreprinten_US
dc.identifier.doi10.1021/acs.inorgchem.0c02973
local.author.affiliationFaculty of Scienceen_US


Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record