التفاصيل البيبلوغرافية
| العنوان: |
Next Generation Cuprous Phenanthroline MLCT Photosensitizer Featuring Cyclohexyl Substituents. |
| المؤلفون: |
Rosko MC; Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, United States., Wells KA; Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, United States., Hauke CE; Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, United States., Castellano FN; Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, United States. |
| المصدر: |
Inorganic chemistry [Inorg Chem] 2021 Jun 21; Vol. 60 (12), pp. 8394-8403. Date of Electronic Publication: 2021 Jun 07. |
| نوع المنشور: |
Journal Article |
| اللغة: |
English |
| بيانات الدورية: |
Publisher: American Chemical Society Country of Publication: United States NLM ID: 0366543 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1520-510X (Electronic) Linking ISSN: 00201669 NLM ISO Abbreviation: Inorg Chem Subsets: PubMed not MEDLINE; MEDLINE |
| أسماء مطبوعة: |
Original Publication: [Easton, Pa.] American Chemical Society. |
| مستخلص: |
A new long-lived, visible-light-absorbing homoleptic Cu(I) metal-to-ligand charge transfer (MLCT) photosensitizer, [Cu(dchtmp) 2 ]PF 6 (dchtmp = 2,9-dicyclohexyl-3,4,7,8-tetramethyl-1,10-phenanthroline), has been synthesized, structurally characterized, and evaluated in terms of its molecular photophysics, electrochemistry, and electronic structure. Static and time-resolved transient absorption (TA) and photoluminescence (PL) spectroscopy measured on the title compound in CH 2 Cl 2 (τ = 2.6 μs, Φ PL = 5.5%), CH 3 CN (τ = 1.5 μs, Φ PL = 2.6%), and THF (τ = 2.0 μs, Φ PL = 3.7%) yielded impressive photophysical metrics even when dissolved in Lewis basic solvents. The combined static spectroscopic data along with ultrafast TA experiments revealed that the pseudo-Jahn-Teller distortion and intersystem crossing dynamics in the MLCT excited state displayed characteristics of being sterically arrested throughout its evolution. Electrochemical and static PL data illustrate that [Cu(dchtmp) 2 ]PF 6 is a potent photoreductant (-1.77 V vs Fc +/0 in CH 3 CN) equal to or greater than all previously investigated homoleptic Cu(I) diimine complexes. Although we successfully prepared the cyclopentyl analog dcptmp (2,9-dicyclopentyl-3,4,7,8-tetramethyl-1,10-phenanthroline) using the same C-C radical coupling photochemistry as dchtmp, the corresponding Cu(I) complex could not be isolated due to the steric hindrance presented at the metal center. Ultimately, the successful preparation of [Cu(dchtmp) 2 ] + represents a major step forward for the design and discovery of novel earth-abundant photosensitizers made possible through a newly conceived ligand synthetic strategy. |
| تواريخ الأحداث: |
Date Created: 20210607 Latest Revision: 20210621 |
| رمز التحديث: |
20240628 |
| DOI: |
10.1021/acs.inorgchem.1c01242 |
| PMID: |
34097407 |
| قاعدة البيانات: |
MEDLINE |
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