Theoretical studies of COOH group effect on the performance of rhenium (I) tricarbonyl complexes with bispyridine sulfur-rich core ligand as dyes in DSSC

Abstract

The series of rhenium (I) tricarbonyl mixedligand complexes ReCl(CO) 3 (H n bpydt) (n = 2, 1; n = 4, 2; bpy = bispyridine, dt = 1,3-dithiole) and ReCl(CO) 3 (H n bpyTTF) (n = 2, 3; n = 3, 4; TTF = Tetrathiafulvalene) have been investigated theoretically to explore the effect of COOH functional group on their electronic structures, spectroscopic properties and their properties as dye in a solar cell. The calculated geometry structure and absorption spectrum of 1 and 3 are generally consistent with the experimental results. By attaching the COOH groups on both bpy and dt (TTF in 4) moiety in 2, the nature of LUMO is also contributed by both p*(bpy) and p*(dt) (p*(TTF) in 4), and the absorptions have an obvious red shift compared with 1 and 3. In addition, it can be found that the transition terminates at the orbital populated by the COOH-appended moieties, and the performance of 2 and 4 in the dye-sensitized solar cell can be enhanced as compared with 1 and 3.

Novel improvements in the sensitizers of dye-sensitized solar cells for enhancement in efficiency-a review

“…The obtained efficiency was found to be 1.72%, 1.46%, and 1.43%, respectively [44]. They found from their studies that by introducing COOH groups, the improvement in absorption properties was found for the designed rhenium sensitizers [45]. In addition, they also studied the effect of COOH group on the electronic and spectroscopic properties of the dyes based on ReCl (CO) 3 (H n bpydt) and ReCl(CO) 3 (H n bpyTTF) as these sensitizers contain multi-sulfur atom at its core, which puts an adverse effect on the overall efficiency of DSSC as sulfur is a poor photosensitizer.…”

“…In addition, they also studied the effect of COOH group on the electronic and spectroscopic properties of the dyes based on ReCl (CO) 3 (H n bpydt) and ReCl(CO) 3 (H n bpyTTF) as these sensitizers contain multi-sulfur atom at its core, which puts an adverse effect on the overall efficiency of DSSC as sulfur is a poor photosensitizer. They found from their studies that by introducing COOH groups, the improvement in absorption properties was found for the designed rhenium sensitizers [45]. Platinum metal-based dyes have also been employed as sensitizers for DSSCs, like square planar platinum (II) dyes with 4, 4′-dicarboxy-2, 2′ bipyridine and quinoxalline-2, 3′-dithiolate ligands.…”

Photoinduced Processes in Rhenium(I) Terpyridine Complexes Bearing Remote Amine Groups: New Insights from Transient Absorption Spectroscopy

“…The first report on the photoluminescence of Re(I) carbonyl complexes fac -[ReX(CO) 3 (N ∩ N)] with 1,10-phenanthroline and its derivatives in solution at room temperature, ascribed to the 3 MLCT [d(Re)–π phen ] excited-state origin, was published in 1974 [ 1 ]. Since this groundbreaking work of Wrighton and Morse, neutral and monocationic complexes of type fac -[ReX(CO) 3 (N ∩ N)] n (N ∩ N = diamine, X = halides, pseudohalides, pyridine, imidazole, and related N-heterocycles, n = 0 or 1+) have become a topic of intense research due to their intriguing photoluminescent properties [ 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 ] and potential applications for photocatalytic carbon dioxide reduction [ 20 , 21 , 22 , 23 ], organic light-emitting diodes [ 24 , 25 , 26 , 27 , 28 , 29 ], solar energy conversion [ 30 , 31 , 32 , 33 ], and medicinal applications [ 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 ]. Taking advantage of the relatively simple synthetic procedur...…”