502622-86-8Relevant academic research and scientific papers
2,2’:6’,2’’-Terpyridine derivative with tetrazole motif and its analogues with 2-pyrazinyl or 2-thiazolyl substituents – Experimental and theoretical investigations
Zych, Dawid,Slodek, Aneta,Ma?ecki, Jan Grzegorz
, (2020)
The synthesis of 4’-[4-(2-decyl-1,3,4-tetrazol-5-yl)phenyl]-2,2’:6’,2’’-terpyridine and its analogues which contain substituted at the central pyridine ring (positions 2 and 6) 2-pyrazinyl or 2-thiazolyl groups is reported. Photophysical, optical studies
Is Gelation Behavior Predictable through a Crystal Engineering Approach? A Case Study in Four Similar Coordination Compounds
Khavasi, Hamid Reza,Esmaeili, Maryam
, p. 4660 - 4671 (2019)
In this paper, a detailed study on the gelation properties of a series of terpyridine and dipyrazine-pyridine ligands in the presence of metal salts is reported. To reveal the driving forces for the self-assembly of the metallogelators, their crystal stru
Living Long and Prosperous: Productive Intraligand Charge-Transfer States from a Rhenium(I) Terpyridine Photosensitizer with Enhanced Light Absorption
Fernández-Terán, Ricardo,Sévery, Laurent
supporting information, p. 1334 - 1343 (2020/10/09)
The ground- and excited-state properties of six rhenium(I) κ2N-tricarbonyl complexes with 4′-(4-substituted-phenyl)terpyridine ligands bearing substituents of different electron-donating abilities were evaluated. Significant modulation of the electrochemical potentials and a nearly 4-fold variation of the triplet metal-to-ligand charge-transfer (3MLCT) lifetimes were observed upon going from CN to OMe. With the more electron-donating NMe2group, we observed in the κ2N complex the appearance of a very strong absorption band, red-shifted by ca. 100 nm with respect to the other complexes. This was accompanied by a dramatic enhancement of the excited-state lifetime (380 vs 1.5 ns), and a character change from 3MLCT to intraligand charge transfer (3ILCT), despite the remote location of the substituent. The dynamics and character of the excited states of all complexes were assigned by combining transient IR spectroscopy, IR spectroelectrochemistry, and (time-dependent) density functional theory calculations. Selected complexes were evaluated as photosensitizers for hydrogen production, with the κ2N-NMe2complex resulting in a stable and efficient photocatalytic system reaching TONRevalues of over 2100, representing the first application of the 3ILCT state of a rhenium(I) carbonyl complex in a stable photocatalytic system.
Multi-Mode Color-Tunable Long Persistent Luminescence in Single-Component Coordination Polymers
Wang, Zheng,Zhu, Cheng-Yi,Mo, Jun-Ting,Xu, Xian-Yan,Ruan, Jia,Pan, Mei,Su, Cheng-Yong
supporting information, p. 2526 - 2533 (2020/12/07)
Materials with tunable long persistent luminescence (LPL) properties have wide applications in security signs, anti-counterfeiting, data encrypting, and other fields. However, the majority of reported tunable LPL materials are pure organic molecules or polymers. Herein, a series of metal-organic coordination polymers displaying color-tunable LPL were synthesized by the self-assembly of HTzPTpy ligand with different cadmium halides (X=Cl, Br, and I). In the solid state, their LPL emission colors can be tuned by the time-evolution, as well as excitation and temperature variation, realizing multi-mode dynamic color tuning from green to yellow or green to red, and are the first such examples in single-component coordination polymer materials. Single-crystal X-ray diffraction analysis and theoretical calculations reveal that the modification of LPL is due to the balanced action from single molecule and aggregate triplet excited states caused by an external heavy-atom effect. The results show that the rational introduction of different halide anions into coordination polymers can realize multi-color LPL.
Coordination Environment Prevents Access to Intraligand Charge-Transfer States through Remote Substitution in Rhenium(I) Terpyridinedicarbonyl Complexes
Fernández-Terán, Ricardo J.,Sévery, Laurent
, p. 1325 - 1333 (2021/01/11)
Six rhenium(I) κ3N-dicarbonyl complexes with 4′-(4-substituted phenyl)terpyridine ligands were evaluated in their ground and excited states. These complexes, bearing substituents of different electron-donating strengths - from CN to NMe2 - were studied by a combination of transient IR (TRIR), electrochemistry, and IR spectroelectrochemistry, as well as time-dependent density functional theory (TD-DFT). They exhibit panchromatic absorption and can act as stronger photoreductants than their tricarbonyl counterparts. The ground- and excited-state potentials, absorption maxima, and lifetimes (250-750 ps) of these complexes correlate well with the Hammett σp substituent constants, showing the systematic effect of remote substitution in the ligand framework. TRIR spectroscopy allowed us to assign the lowest singlet and triplet excited states to a metal-to-ligand charge-transfer (MLCT) character. This result contrasts our previous report on analogous κ2N-tricarbonyl complexes, where remote substitution switched the character from MLCT to intraligand charge transfer. With the help of TD-DFT calculations, we dissect the geometric and electronic effects of coordination of the third pyridine, local symmetries, and increasing conjugation length. These results give valuable insights for the design of complexes with long-lived triplet excited states and enhanced absorption throughout the visible spectrum, while showcasing the boundaries of the excited-state switching strategy via remote substitution.
A facile route to sterically hindered and non-hindered 4′-aryl-2, 2′:6′,2″-terpyridines
Wang, Jianhua,Hanan, Garry S.
, p. 1251 - 1254 (2007/10/03)
A facile one-pot synthesis of 4′-aryl-2,2′:6′,2″- terpyridines from aryl aldehydes and 2-acetylpyridine is presented. The synthesis of terpyridines incorporating sterically hindered aryl groups, such as the 9-anthryl group, can also be readily synthesized using this method.
The synthesis of 4′-aryl substituted terpyridines by Suzuki cross-coupling reactions: Substituent effects on ligand fluorescence
Goodall, Wendy,Wild, Kerstin,Arm, Kathryn J.,Williams, J.A. Gareth
, p. 1669 - 1681 (2007/10/03)
Several 4′-aryl-substituted 2,2′:6′,2″-terpyridines (tpy-C6H4R) have been prepared by palladium-catalysed cross-coupling of 4′-bromoterpyridine or 4′-triflate-terpyridine (triflate = trifluoromethylsulfonyloxy) with aryl boronic acids or esters, RC6H4B(OR′)2 (R = H, m-NH2, p-CHO, -NO2, -CN, -NMe2, -NPh2). The new ligand 4′-mesityl-terpyridine (mesityl = 2,4,6-trimethylphenyl) was prepared in the same way. Similarly, 4′-bromophenylterpyridine (tpy-φ-Br) has been cross-coupled with aryl halides to generate several new biaryl-substituted terpyridines (tpy-φ-C6H4R where R = H, p-CN, NMe2, NPh2), together with two related compounds with pendent 3- or 4-pyridyl groups (tpy-φ-C6H4-py). For selected compounds, the alternative coupling strategy of reaction of a terpyridine-4-boronate or terpyridine-4-phenylboronate with the appropriate aryl halide has also been investigated (e.g. to prepare tpy-φ-C6H4NO2), but was generally found to be less satisfactory. All of the compounds are fluorescent in the UV region of the spectrum, the biaryl-substituted compounds being only slightly red-shifted compared to the monoaryl systems, but with the further red-shift that accompanies protonation being more significant for the former. Fluorescence lifetimes in solution are in the range 1-5 ns. The emission spectra of the aminobiphenyl-substituted compounds (tpy-φ-C6H4NR″2, where R″ = Me or Ph) display a large red-shift with increasing solvent polarity, suggesting the involvement of an intramolecular charge transfer state, as found previously for the two analogues omitting the phenyl ring (tpy-C6H4NR″2). In contrast to the latter, however, protonation or binding of a Lewis acidic metal ion to the aminobiphenyl compounds serves to quench almost completely their emission.
