The Versatile SALSAC Approach to Heteroleptic Copper(I) Dye Assembly in Dye-Sensitized Solar Cells

Malzner, Frederik J.; Housecroft, Catherine E.; Constable, Edwin C.

doi:10.3390/inorganics6020057

Cited by 20 publications

(38 citation statements)

References 45 publications

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“…Based on our previous experience of functionalizing TiO 2 surfaces, 19,20,24 anchoring ligands 1 and 4 (Scheme 1) were selected for the present investigation to provide a comparison of carboxylic versus phosphonic acid anchors. The DSC community consider that phosphonic acid anchors give more stable attachment to TiO 2 surfaces than carboxylic acids.…”

Section: Choice Of Anchoring Ligandsmentioning

confidence: 99%

“…Our initial attempts to replicate TiO 2 surface-functionalization using commercial NPs (AEROXIDE TiO 2 P25) suspended in DMSO in place of screen-printed and annealed (commercial or in-house fabricated) surfaces following previously published protocols 20,52 samples. Apart from small changes (<0.1 ppm) in the chemical shis of signals, the spectra are essentially identical and the signals remain sharp.…”

Section: Nanoparticle Activation and General Procedures For Functionalmentioning

confidence: 99%

“…16 In most cases the methods are either highly specic to the target structure, are dependent upon the preparation of complex soluble or volatile covalent structures or have signicant elements of serendipity in the outcome. 17 In the context of our research into dye-sensitized solar cells (DSCs), we developed a methodology [18][19][20] which we have termed 'surfaces-as-ligands, surfaces-as-complexes' (SALSAC). This extends 'simple' self-assembly and self-organization at surfaces to the stepwise and hierarchical building up of new pre-dened and easily tailored architectures.…”

Section: Introductionmentioning

confidence: 99%

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The SALSAC approach: comparing the reactivity of solvent-dispersed nanoparticles with nanoparticulate surfaces

et al. 2020

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Section: Choice Of Anchoring Ligandsmentioning

confidence: 99%

Section: Nanoparticle Activation and General Procedures For Functionalmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The SALSAC approach: comparing the reactivity of solvent-dispersed nanoparticles with nanoparticulate surfaces

et al. 2020

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“…The HETPHEN (HETeroleptic PHENanthroline) approach utilized by Odobel and coworkers [21,22] employs sterically demanding substituents in the 6,6 -positions of a bpy ligand, or in the 2,9-positions of phen, to isolate heteroleptic [Cu(L)(L )][X] complexes and stabilize them with respect to ligand redistribution in solution. In contrast, we have adopted the "surfaces-as-ligands, surfaces-as-complexes" (SALSAC) approach [23,24], which is extremely versatile and allows heteroleptic copper(I) dyes to be assembled directly on a semiconductor surface by ligand exchange between an anchored diimine ligand and a homoleptic copper(I) complex (Scheme 1). A class of ligands that has proven beneficial in bis(diimine)copper(I) dyes is based upon 4,4 -styryl-6,6 -dimethyl-2,2 -bipyridine in which the R group in Scheme 2 is systematically varied.…”

Section: Introductionmentioning

confidence: 99%

Schiff Base Ancillary Ligands in Bis(diimine) Copper(I) Dye-Sensitized Solar Cells

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Cortés

Prescimone

et al. 2020

IJMS

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Five 6,6′-dimethyl-2,2′-bipyridine ligands bearing N-arylmethaniminyl substituents in the 4- and 4′-positions were prepared by Schiff base condensation in which the aryl group is Ph (1), 4-tolyl (2), 4-tBuC6H4 (3), 4-MeOC6H4 (4), and 4-Me2NC6H4 (5). The homoleptic copper(I) complexes [CuL2][PF6] (L = 1–5) were synthesized and characterized, and the single crystal structure of [Cu(1)2][PF6]·Et2O was determined. By using the “surfaces-as-ligands, surfaces-as-complexes” (SALSAC) approach, the heteroleptic complexes [Cu(6)(Lancillary)]+ in which 6 is the anchoring ligand ((6,6′-dimethyl-[2,2′-bipyridine]-4,4′-diyl)bis(4,1-phenylene))bis(phosphonic acid)) and Lancillary = 1–5 were assembled on FTO-TiO2 electrodes and incorporated as dyes into n-type dye-sensitized solar cells (DSCs). Data from triplicate, fully-masked DSCs for each dye revealed that the best-performing sensitizer is [Cu(6)(1)]+, which exhibits photoconversion efficiencies (η) of up to 1.51% compared to 5.74% for the standard reference dye N719. The introduction of the electron-donating MeO and Me2N groups (Lancillary = 4 and 5) is detrimental, leading to a decrease in the short-circuit current densities and external quantum efficiencies of the solar cells. In addition, a significant loss in open-circuit voltage is observed for DSCs sensitized with [Cu(6)(5)]+, which contributes to low values of η for this dye. Comparisons between performances of DSCs containing [Cu(6)(1)]+ and [Cu(6)(4)]+ with those sensitized by analogous dyes lacking the imine bond indicate that the latter prevents efficient electron transfer across the dye.

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“…Phosphonic acid anchoring groups have been shown to bind more strongly to semiconductor oxide surfaces than carboxylic acids and we have been particularly interested in the use of the phosphonic acid anchoring ligands shown in Scheme 1. The phosphonic acid anchor has been shown to be effective in complexes containing {Ru(bpy) 2 (CˆN)} + [11,12], {Cu(bpy) 2 } + [13,14], and {Zn(tpy) 2 } + [15,16] cores (CˆN = a cyclometallating ligand such as the conjugate base of 2-phenylpyridine, bpy = 2,2 -bipyridine), and we have demonstrated that, in copper-based dyes, the presence of both a 1,4-phenylene spacer between a bpy metal-binding domain and the phosphonic acid is beneficial to DSC performance [17]. The tpy derivative shown in Scheme 1 has been used in a number of {Ru(tpy) 2 } + -and {Zn(tpy) 2 } + -based dyes [15][16][17][18][19][20][21][22], and theoretical studies indicate that the presence of the 1,4-phenylene spacer enhances the rate of electron-transfer across the dye/semiconductor interface [23].…”

Section: Introductionmentioning

confidence: 99%

Where Are the tpy Embraces in [Zn{4′-(EtO)2OPC6H4tpy}2][CF3SO3]2?

et al. 2018

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In this paper, the bromo-and phosphonate-ester-functionalized complexes [Zn(1) 2 ] [CF 3 SO 3 ] 2 and [Zn(2) 2 ][CF 3 SO 3 ] 2 (1 = 4 -(4-bromophenyl)-2,2 :6 ,2 -terpyridine, 2 = diethyl (4-([2,2 : 6 ,2 -terpyridin]-4 -yl)phenyl)phosphonate) are reported. The complexes have been characterized by electrospray mass spectrometry, IR and absorption spectroscopies, and multinuclear NMR spectroscopy. The single-crystal structures of [Zn (1) 2 ][CF 3 SO 3 ] 2 . MeCN .1 / 2 Et 2 O and [Zn(2) 2 ][CF 3 SO 3 ] 2 have been determined and they confirm {Zn(tpy) 2 } 2+ cores (tpy = 2,2 :6 ,2 -terpyridine). Ongoing from X = Br to P(O)(OEt) 2 , the {Zn(4 -XC 6 H 4 tpy) 2 } 2+ unit exhibits significant "bowing" of the backbone, which is associated with changes in packing interactions. The [Zn(1) 2 ] 2+ cations engage in head-to-tail 4 -Phtpy...4 -Phtpy embraces with efficient pyridine...phenylene π-stacking interactions. The [Zn(2) 2 ] 2+ cations pack with one of the two ligands involved in pyridine...pyridine π-stacking; steric hindrance between one C 6 H 4 PO(OEt) 2 group and an adjacent pair of π-stacked pyridine rings results in distortion of backbone of the ligand. This report is the first crystallographic determination of a salt of a homoleptic [M{4 -(RO) 2 OPC 6 H 4 tpy} 2 ] n+ cation. Crystals 2018, 8, x FOR PEER REVIEW 2 of 11 presence of the 1,4-phenylene spacer enhances the rate of electron-transfer across the dye/semiconductor interface [23]. Scheme 1. Examples of anchoring ligands (cyclometallating H(C^N), bpy N^N, and tpy N^N^N) used in sensitizers in metal complex dyes in dye-sensitized solar cells.Despite the interest in sensitizers based on polypyridine metal complexes incorporating phosphonic acid anchors, there is remarkably little crystallographic data available to provide insights into structural details, in particular, packing interactions that may influence aggregation of the surface-adsorbed species. A search of the CSD (v. 5.40, November 2018 [24] for metal-bonded {4′-O3P-tpy} or {4′-O3P-C6H4tpy} units gave surprisingly few hits [25][26][27][28][29][30][31][32], with only one featuring a 1,4-phenylene spacer [32]. It is also interesting to note that all of the reported structures relate to phosphonate esters rather than the parent phosphonic acids, and that the majority of the studies were motivated by application of the complexes as logic gates, photosensitizers, and catalysts. Here, we report the syntheses and single-crystal structures of the two zinc(II) complexes [Zn(1)2][CF3SO3]2 and [Zn(2)2][CF3SO3]2 (where ligands 1 and 2 are defined in Scheme 2) and investigate the effects that the phosphonate ester group has on intermolecular interactions in the solid state.Scheme 2. Structures of the ligands 1 and 2. Materials and Methods General1 H, 13 C, and 31 P NMR spectra were recorded on a Bruker Avance III-500 spectrometer (Bruker BioSpin AG, Fällanden, Switzerland) at 298 K. The 1 H and 13 C NMR chemical shifts were referenced with respect to residual solvent peaks (δ TMS = 0), and 31 P shift with respec...

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The Versatile SALSAC Approach to Heteroleptic Copper(I) Dye Assembly in Dye-Sensitized Solar Cells

Cited by 20 publications

References 45 publications

The SALSAC approach: comparing the reactivity of solvent-dispersed nanoparticles with nanoparticulate surfaces

The SALSAC approach: comparing the reactivity of solvent-dispersed nanoparticles with nanoparticulate surfaces

Schiff Base Ancillary Ligands in Bis(diimine) Copper(I) Dye-Sensitized Solar Cells

Where Are the tpy Embraces in [Zn{4′-(EtO)2OPC6H4tpy}2][CF3SO3]2?

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