Alkyl chain-functionalized hole-transporting domains in zinc(II) dye-sensitized solar cells

Hostettler, Nik; Fürer, Sebastian O.; Bozic-Weber, Biljana; Constable, Edwin C.; Housecroft, Catherine E.

doi:10.1016/j.dyepig.2015.01.008

Cited by 7 publications

(10 citation statements)

References 33 publications

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“…We have shown that by generating a new library of anchoring ligands 66 and 67 and ancillary ligands 68 -75 based upon tpy metal-binding domains ( Figure 37) the strategy can be extended to octahedral metal centres and we have given proof of concept with zinc(II) surface bound materials. In this case, although the d 10 zinc(II) centre does not give strong MLCT bands, by using ancillary ligands which absorbed strongly in the visible, it was possible to fabricate functioning DSCs (199,200,201).…”

Section: The Futurementioning

confidence: 99%

A Journey From Solution Self-Assembly to Designed Interfacial Assembly

Constable

2018

Advances in Inorganic Chemistry

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This article describes the development of concepts in metallosupramolecular chemistry. In particular, the transfer of the concepts from solution phase to metallosupramolecular chemistry at solid-fluid interfaces is discussed. The concept of metal-binding domains is quantified and used for the design of ligands for specific supramolecular applications. The use of weak interactions for the investigation of surface supramolecular chemistry is presented followed by the "surfaces as ligands, surfaces as complexes" approach for the design of functional devices. This conceptual development is placed in the concept the author's own laboratory.This account is about a journey from "traditional" coordination chemistry, through solution phase supramolecular chemistry to the use of the paradigms and methodologies of self-organization and self-assembly in the construction of ordered and hierarchical structures at solid-fluid interfaces. At the end phase of this journey, interactions with atomically well-defined and low-dimensional surfaces as well-as complex nanostructured surfaces will be considered. FROM COORDINATION CHEMISTRY TO METALLOSUPRAMOLECULAR CHEMISTRY Coordination chemistry as molecular recognition"What goes around comes around" -this journey begins with the design of 2,2'bipyridine ligands for application in what came to be known as dye-sensitized solar cells and ends in the development of new methodologies for the design of these and related systems. Rutile (TiO 2 ) is a semiconductor with a band gap of » 3.0 eV and exhibits no photocurrent upon irradiation with light l > 450 nm. In contrast, the complex [Ru(bpy) 2 (1)] exhibits a typical {Ru II (bpy) 3 } absorption close to 450 nm.The complex [Ru(bpy) 2 (1)] binds to the surface of single crystal rutile and acts as a photosensitizer, allowing the photoinjection of electrons directly into the conduction band upon irradiation with visible light l > 450 nm (Figure 1) (3). The photocurrents were modest and it was only when Grätzel used this strategy for the modification of nanostructured TiO 2 surfaces, allowing very high dye-loading, that the method became viable (4,5,6).

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Section: The Futurementioning

confidence: 99%

A Journey From Solution Self-Assembly to Designed Interfacial Assembly

Constable

2018

Advances in Inorganic Chemistry

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“…Heteroleptic surface-bound [Zn(L anchor )(L ancillary )] 2+ complexes were assembled in a stepwise manner on an FTO/TiO 2 electrode using our 'surfaces-as-ligands' strategy. 17,28 The electrode was initially immersed in a DMSO solution of 1 27 or 2 48 (Scheme 1), and then the ligand-functionalized electrode was dipped into an EtOH solution of ZnCl 2 to give a surface bound [Zn(L anchor )Cl 2 ] complex ( Fig. 1).…”

Section: Dsc Fabrication and Performancementioning

confidence: 99%

“…However, for all the dyes, performance was disappointingly poor, although better than with rst generation ancillary ligands 4-7. 28 In order to verify the validity of the DSC measurements, parameters of two blank cells (i.e. FTO/TiO 2 without adsorbed dye) were recorded (Table 4).…”

Section: Dsc Fabrication and Performancementioning

confidence: 99%

“…10 Copper(I) sensitizers [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] feature strongly, but we have also reported the successful use of {Zn(tpy) 2 } 2+ -containing dyes (tpy ¼ 2,2 0 :6 0 ,2 00 -terpyridine), albeit with low photon-to-current conversion efficiencies. 27, 28 The lability of both copper(I) and zinc(II) complexes permits sequential assembly of photoactive dyes on a semiconductor surface using the 'surface-as-ligand, surface-as-complex' methodology; 17 ligand exchange is rapid for copper(I) but slower for zinc(II). Fig.…”

Section: Introductionmentioning

confidence: 99%

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Dye-sensitized solar cells with hole-stabilizing surfaces: “inorganic” versus “organic” strategies

et al. 2015

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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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Alkyl chain-functionalized hole-transporting domains in zinc(II) dye-sensitized solar cells

Cited by 7 publications

References 33 publications

A Journey From Solution Self-Assembly to Designed Interfacial Assembly

A Journey From Solution Self-Assembly to Designed Interfacial Assembly

Dye-sensitized solar cells with hole-stabilizing surfaces: “inorganic” versus “organic” strategies

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

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