Probing the excited state nature of coordination complexes with blended organic and inorganic chromophores using vibrational spectroscopy

Horvath, Raphael; Huff, Gregory S.; Gordon, Keith C.; George, Michael W.

doi:10.1016/j.ccr.2016.04.007

Cited by 23 publications

(24 citation statements)

References 223 publications

(140 reference statements)

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“…By scanning the absorption profile, and monitoring the resonantly enhanced vibrations, the nature of the electronic transitions occurring can be probed. In the context of this study charge transfer excitation could lead to the enhancement of either donor or acceptor modes, enhancement of bridging modes would be consistent with the bridge playing a role in this transition [ 50 , 52 , 53 , 54 , 55 ].…”

Section: Resultsmentioning

confidence: 61%

Modulation of Donor-Acceptor Distance in a Series of Carbazole Push-Pull Dyes; A Spectroscopic and Computational Study

et al. 2018

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A series of eight carbazole-cyanoacrylate based donor-acceptor dyes were studied. Within the series the influence of modifying the thiophene bridge, linking donor and acceptor and a change in the nature of the acceptor, from acid to ester, was explored. In this joint experimental and computational study we have used electronic absorbance and emission spectroscopies, Raman spectroscopy and computational modeling (density functional theory). From these studies it was found that extending the bridge length allowed the lowest energy transition to be systematically red shifted by 0.12 eV, allowing for limited tuning of the absorption of dyes using this structural motif. Using the aforementioned techniques we demonstrate that this transition is charge transfer in nature. Furthermore, the extent of charge transfer between donor and acceptor decreases with increasing bridge length and the bridge plays a smaller role in electronically mixing with the acceptor as it is extended.

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Section: Resultsmentioning

confidence: 61%

Modulation of Donor-Acceptor Distance in a Series of Carbazole Push-Pull Dyes; A Spectroscopic and Computational Study

et al. 2018

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“…Resonance Raman spectroscopy (RRS) may be used to provide insight into the electronic nature and localization of the chromophores giving rise to the electronic spectra. ,− For these compounds the RRS spectra were collected from 355 to 491 nm in both CH 2 Cl 2 (Figure ) and MeCN (Figures S16 and S17). From the experimental RRS data and computational modeling the nature of the lowest energy transitions may be assigned.…”

Section: Results and Discussionmentioning

confidence: 99%

Excited-State Switching in Rhenium(I) Bipyridyl Complexes with Donor–Donor and Donor–Acceptor Substituents

et al. 2021

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The optical properties of two Re(CO)3(bpy)Cl complexes in which the bpy is substituted with two donor (triphenylamine, TPA, ReTPA2) as well as both donor (TPA) and acceptor (benzothiadiazole, BTD, ReTPA-BTD) groups are presented. For ReTPA2 the absorption spectra show intense intraligand charge-transfer (ILCT) bands at 460 nm with small solvatochromic behavior; for ReTPA-BTD the ILCT transitions are weaker. These transitions are assigned as TPA → bpy transitions as supported by resonance Raman data and TDDFT calculations. The excited-state spectroscopy shows the presence of two emissive states for both complexes. The intensity of these emission signals is modulated by solvent. Time-resolved infrared spectroscopy definitively assigns the excited states present in CH2Cl2 to be MLCT in nature, and in MeCN the excited states are ILCT in nature. DFT calculations indicated this switching with solvent is governed by access to states controlled by spin–orbit coupling, which is sufficiently different in the two solvents, allowing to select out each of the charge-transfer states.

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“…In contrast, polyenes consist of an even number of π centers and the same number of π electrons. , Consequently, polyenes and polymethines differ considerably in their electronic structure and hence their light absorption properties. Polymethine chromophores have been incorporated in metal complexes, usually by attachment of the chromophore to the coordinating ligands. − In 4 H -imidazolate complexes, however, the organic chromophore is directly coordinated to the metal center. For instance, in Ru(II) 4 H -imidazolate complexes, mixing of the organic and inorganic chromophores was observed. − …”

Section: Introductionmentioning

confidence: 99%

Role of MLCT States in the Franck–Condon Region of Neutral, Heteroleptic Cu(I)–4H-imidazolate Complexes: A Spectroscopic and Theoretical Study

et al. 2020

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The impact of the electronic structure of a series of 4H-imidazolate ligands in neutral, heteroleptic Cu(I) complexes is investigated. Remarkable broad and strong ligand-dependent absorption in the visible range of the electromagnetic spectrum renders the studied complexes promising photosensitizers for photocatalytic applications. The electronic structure of the Cu(I) complexes and the localization of photoexcited states in the Franck–Condon region are unraveled by means of UV–vis absorption and resonance Raman (rR) spectroscopy supported by time-dependent density functional theory (TD-DFT) calculations. The visible absorption bands stem from a superposition of bright metal-to-ligand charge-transfer (MLCT) and π–π* as well as weakly absorbing MLCT states. Additionally, the analysis of involved molecular orbitals and rR spectra upon excitation of MLCT and π–π* states highlights the impact of the electronic structure of the 4H-imidazolate ligands on the properties of the corresponding Cu(I) complexes to avail a toolbox for predictive studies and efficient complex design.

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Probing the excited state nature of coordination complexes with blended organic and inorganic chromophores using vibrational spectroscopy

Cited by 23 publications

References 223 publications

Modulation of Donor-Acceptor Distance in a Series of Carbazole Push-Pull Dyes; A Spectroscopic and Computational Study

Modulation of Donor-Acceptor Distance in a Series of Carbazole Push-Pull Dyes; A Spectroscopic and Computational Study

Excited-State Switching in Rhenium(I) Bipyridyl Complexes with Donor–Donor and Donor–Acceptor Substituents

Role of MLCT States in the Franck–Condon Region of Neutral, Heteroleptic Cu(I)–4H-imidazolate Complexes: A Spectroscopic and Theoretical Study

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