The surprising lability of bis(2,2’:6’,2’’-terpyridine)- chromium(III) complexes

The complex [Cr(tpy)(O3SCF3)3] (tpy = 2,2′:6′,2′′-terpyridine) is readily made from [Cr(tpy)Cl3] and is a convenient precursor to [Cr(tpy)2][PF6]3 and to [Cr(tpy)(4′-(4-tolyl)tpy)][PF6]3 and [Cr(tpy)(5,5′′-Me2tpy)][PF6]3 (4′-(4-tolyl)tpy = 4′-(4-tolyl)-2,2′:6′,2′′-terpyridine; 5,5′′-Me2tpy = 5,5′′-dimethyl-2,2′:6′,2′′-terpyridine); these are the first examples of heteroleptic bis(tpy) chromium(III) complexes. The single crystal structures of 2{[Cr(tpy)2][PF6]3}·5MeCN, [Cr(tpy)(4′-(4-tolyl)tpy)][PF6]3·3MeCN and [Cr(tpy)(5,5′′-Me2tpy)][PF6]3·3MeCN have been determined. Each cation contains the expected octahedral {Cr(tpy)2}3+ unit; in all three structures, the need to accommodate three anions per cation and the solvent molecules prevents the formation of a grid-like array of cations that is typical of many lattices containing {M(tpy)2}2+ motifs. Three reversible electrochemical processes are observed for [Cr(tpy)(4′-(4-tolyl)tpy)][PF6]3 and [Cr(tpy)(5,5′′-Me2tpy)][PF6]3, consistent with those documented for [Cr(tpy)2]3+. At pH 6.36, aqueous solutions of [Cr(tpy)2][PF6]3 are stable for at least two months. However, contrary to the expectations of the d3 Cr3+ ion being a kinetically inert metal centre, the tpy ligands in [Cr(tpy)2]3+are labile in the presence of base; absorption and 1H NMR spectroscopies have been used to monitor the effects of adding NaOH to aqueous and CD3OD solutions, respectively, of the homo- and heteroleptic complexes. Ligand dissociation is also observed when [Bu4N]F is added to CD3OD solutions of the complexes, but in aqueous solution, [Cr(tpy)2][PF6]3 is stable in the presence of fluoride ion

The d(10) route to dye-sensitized solar cells: step-wise assembly of zinc(II) photosensitizers on TiO2 surfaces

Dye-sensitized solar cells have been assembled using a sequential approach: a TiO2 surface was functionalized with an anchoring ligand, followed by metallation with Zn(OAc)(2) or ZnCl2, and subsequent capping with a chromophore functionalized 2,2`:6`,2 ``-terpyridine; the DSCs exhibit surprisingly good efficiencies confirming the effectiveness of the new strategy for zinc-based DSC fabrication

Copper-based Dye-sensitized Solar Cells with Quasi-Solid Nano Cellulose Composite Electrolytes

The study presented describes the preparation of solvent-free nano composite gel electrolytes in combination with  copper(I)-based dye-sensitized solar cells (DSSCs). The electrolytes comprise poly(ethylene oxide) (PEO) and cellulose nano crystals (CNCs) and an I 3 – /I – redox shuttle. The quasi-solid-state DSSCs show increased photoconversion performance with increased amount of CNC in the electrolyte. DSSC performances measured on the day that the devices are fabricated show that when the electrolyte is composed of 80% CNC, a cell efficiency of 1.09% is reached compared to 1.16% using a standard liquid I 3 – /I – electrolyte. DSSCs containing the nano composites and the copper(I)-based dye show robust stability over time, and after 60 days, DSSCs with the PEO/CNC/I 3 – /I – electrolyte outperform those containing the liquid electrolyt

Constructing chiral MOFs by functionalizing 4,2′:6′,4″-terpyridine with long-chain alkoxy domains: rare examples of neb nets

Reactions of 4′-(4- n alkyloxyphenyl)-4,2′:6′,4″-terpyridines (alkyl = hexyl or nonyl) with CoIJNCS) 2 lead to three structurally characterized chiral 3D assemblies which adopt rare neb topologies. For the n hexyl-functionalized ligands, both enantiomorphic lattices of the neb nets (crystallizing in the tetragonal space groups P4 1 2 1 2 and P4 3 2 1 2, respectively) are presente

[Ir(C^N)2(N^N)]+ emitters containing a naphthalene unit within a linker between the two cyclometallating ligands

The synthesis of four cyclometallated [Ir(C^N) 2 (N^N)][PF 6 ] compounds in which N^N is a substituted 2,2’- -bipyridine (bpy) ligand and the naphthyl-centred ligand 2,7-bis(2-(2-(4-(pyridin-2-yl)phenoxy)ethoxy) ethoxy)naphthalene provides the two cyclometallating C^N units is reported. The iridium( III ) complexes have been characterized by 1 H and 13 C NMR spectroscopies, mass spectrometry and elemental analysis, and their electrochemical and photophysical properties are described. Comparisons are made with a model [Ir(ppy) 2 (N^N)][PF 6 ] compound (Hppy = 2-phenylpyridine). The complexes containing the naphthyl-unit exhibit similar absorption spectra and excitation at 280 nm leads to an orange emission. The incorporation of the naphthalene unit does not lead to a desirable blue contribution to the emission. Density functional theory calculations were performed to investigate the geometries of the complexes in their ground and first triplet excited states, as well as the energies and compositions of the highestoccupied and lowest unoccupied molecular orbital (HOMO and LUMO) manifolds. Trends in the HOMO– LUMO gaps agree with those observed electrochemically. The energy difference between the LUMO and the lowest unoccupied MO located on the naphthyl unit (LUMO+7) is large enough to explain why there is no contribution from the naphthyl-centred triplet excited state to the phosphorescence emission. Singlet excited states were also investigated. Light-emitting electrochemical cells (LECs) using the [Ir(C^N) 2 (N^N)][PF 6 ] and [Ir(ppy) 2 (N^N)][PF 6 ] complexes in the emissive layer were made and evaluated. The presence of the naphthyl-bridge between the cyclometallating units does not significantly alter the device response

Exploring simple ancillary ligands in copper-based dye-sensitized solar cells: effects of a heteroatom switch and of co-sensitization

The copper( I ) complexes [Cu(1) 2 ][PF 6 ], [Cu(2) 2 ][PF 6 ], [Cu(3) 2 ][PF 6 ] and [Cu(4) 2 ][PF 6 ] (1 . 2-(1H-imidazol-2-yl)- 6-methylpyridine, 2 . 2-(6-methylpyridin-2-yl)oxazole, 3 . 2-(6-methylpyridin-2-yl)thiazole and 4 . 2- methyl-6-(1-methyl-1H-imidazol-2-yl)pyridine) are reported. The crystal structures of [Cu(2) 2 ][PF 6 ]$ 0.5CH 2 Cl 2 and [Cu(3) 2 ][PF 6 ] confirm N,N 0 -chelation modes for 2 and 3, and tetrahedral copper( I ). In the solution absorption spectra, the MLCT band shifts to lower energy with a change in heteroatom (O, 424 nm; NH, 435 nm; NMe, 446 nm; S, 465 nm). [Cu(1) 2 ][PF 6 ] and [Cu(4) 2 ][PF 6 ] undergo copper-centred oxidative processes at lower potential than the complexes with O or S heteroatoms. Heteroleptic complexes [Cu(5)(L)] + (5 . ((6,6 0 -dimethyl-[2,2 0 -bipyridine]-4,4 0 -diyl)bis(4,1-phenylene)bis(phosphonic acid)), L . 1–4) were assembled on FTO/TiO 2 electrodes. The shift in the MLCT band (O NH < NMe < S) in the solid-state absorption spectra of the dye-functionalized electrodes parallels that of solution. The photoconversion efficiencies (h) of masked, dye-sensitized solar cells (DSCs) containing [Cu(5)(L)] + (L . 1– 4) dyes and an I/I 3 redox shuttle follow the order [Cu(5)(1)] + (3.03%) > [Cu(5)(3)] + (2.88%) > [Cu(5)(4)] + (2.71%) > [Cu(5)(2)] + (2.62%) relative to 7.55% for N719. Ancillary ligand 1 (with NH) leads to the highest open-circuit voltage (V OC . 608 mV) whilst 3 (S-heteroatom) gives the highest short-circuit current density (J SC . 7.76 mA cm 2 ). The performances of [Cu(5)(1)] + and [Cu(5)(3)] + are understood with the aid of electrochemical impedance spectroscopy (EIS). The DSC with [Cu(5)(1)] + exhibits a high chemical capacitance (C m ) and a low recombination resistance (R rec ); since the latter is offset by a low transport resistance (R tr ), a high J SC and V OC are observed for [Cu(5)(1)] + . DSCs with [Cu(5)(3)] + have the lowest R tr of all four devices. The performance of DSCs sensitized by a combination of [Cu(5)(1)] + and [Cu(5)(3)] + were assessed in order to capitalize upon the high V OC of [Cu(5)(1)] + and the high J SC of [Cu(5)(3)] + . After FTO/ TiO 2 functionalization with anchor 5, the electrodes were treated with a 1 : 1 mix of [Cu(5)(1)] + and [Cu(5)(3)] + or sequentially with [Cu(5)(3)] + then [Cu(5)(1)] + , or [Cu(5)(1)] + then [Cu(5)(3)] + . The DSC performances and the EIS parameters are consistent with competition between 1 and 3 for surface binding-sites; 1 dominates over 3, both in binding and in contribution to the overall photoresponse

Heteroleptic chromium(III) tris(diimine) [Cr(N^N)2(N'^N')]3+ complexes

A series of heteroleptic tris(diimine) complexes of chromium(III) is reported and the crystal structures of {4[Cr(bpy)2(phen)][PF6]3}·11MeCN and 4[Cr(4,4′-Me2bpy)2(bpy)][PF6]3}·12MeCN·H2O are described. The combined effects of a 1:3 cation: anion ratio and lattice solvent molecules are discussed, in particular in the context of the influence on intercation embraces. The presence of the methyl substituents in {4[Cr(4,4′-Me2bpy)2(bpy)][PF6]3}·12MeCN·H2O results in Me–πbpy contacts becoming the dominant packing interactions and in the assembly of motifs distinct from those in {4[Cr(bpy)2(phen)][PF6]3}·11MeCN

Dynamics of First Order Transitions with Gravity Duals

A first order phase transition usually proceeds by nucleating bubbles of the new phase which then rapidly expand. In confining gauge theories with a gravity dual, the deconfined phase is often described by a black hole. If one starts in this phase and lowers the temperature, the usual description of how the phase transition proceeds violates the area theorem. We study the dynamics of this phase transition using the insights from the dual gravitational description, and resolve this apparent contradiction.Comment: 11 pages, 1 figure. v2: minor clarifications, reference adde

Coordination behaviour of 1-(4,2':6',4''-terpyridin-4'-yl)ferrocene and 1-(3,2':6',3''-terpyridin-4'-yl)ferrocene: predictable and unpredictable assembly algorithms

The reaction of 1-(4,2':6',4''-terpyridin-4'-yl)ferrocene ( 2 ) with ZnI 2 leads to [{ZnI 2 ( 2 )} 4 . 1.4MeOH . 0.8H 2 O] which contains a discrete [4+4] metallocycle. Crystal growth experiments demonstrate that reactions of 2 with Zn(OAc) 2 or CuCl 2 result in the formation of single- or double-stranded 1D-polymer chains, respectively, the latter facilitated by the formation of {Cu 2 Cl 4 } dinuclear nodes. Whilst both 2 and its isomer 1-(3,2':6',3''-terpyridin-4'-yl)ferrocene ( 3 ) present V-shaped donor sets, rotation about interannular bonds in 3 generates flexible vectorial properties associated with limiting convergent and divergent orientations of the nitrogen donors. The synthesis and characterization of 3 are described as are reactions of 3 with ZnCl 2 or ZnBr 2 which lead, respectively, to a metallosquare in [{ZnCl 2 ( 3 )} 4 . 3CHCl 3 . 3MeOH] or a helical polymer in [{ZnBr 2 ( 3 )} . MeOH] n . The tight pitch of the helix in the latter (8.7879(9) Å) is controlled by a combination of the orientations of the N,N ''-donor sets in 3 , and intra-chain π-stacking interactions involving ferrocenyl and pyridine units

4,2':6',4''- and 3,2':6',3''-terpyridines: the conflict between well-defined vectorial properties and serendipity in the assembly of 1D-, 2D- and 3D-architectures

A comparative investigation of the coordination assemblies formed between Co(NCS) 2 and two monotopic 4,2':6',4''-terpyridine (4,2':6',4''-tpy) ligands or two related ditopic ligands is reported. Crystals were grown by layering MeOH solutions of Co(NCS) 2 over a CHCl 3 or 1,2-C 6 H 4 Cl 2 solution of the respective ligand at room temperature. With 4'-(2-methylpyrimidin-5-yl)-4,2':6',4''-terpyridine ( 6 ), the 1D-coordination polymer {[Co 2 (NCS) 4 (MeOH) 4 ( 6 ) 2 ]∙2MeOH∙8H 2 O} n assembles with 6 coordinating only through the outer N-donors of the 4,2':6',4''-tpy unit; coordination by the MeOH solvent blocks two cobalt coordination sites preventing propagation in a higher-dimensional network. A combination of Co(NCS) 2 and 1-(4,2':6',4''-terpyridin-4'-yl)ferrocene ( 7 ) leads to {[Co(NCS) 2 ( 7 ) 2 ]∙4CHCl 3 } n which contains a (4,4) net; the 2D-sheets associate through π-stacking interactions between ferrocenyl and pyridyl units. A 3D-framework is achieved through use of the ditopic ligand 1,4-bis( n propoxy)-2,5-bis(4,2':6',4''-terpyridin-4'-yl)benzene ( 8 ) which acts as a 4-connecting node in {[Co(NCS) 2 ( 8 ) 2 ] . 2C 6 H 4 Cl 2 } n ; the combination of metal and ligand planar 4-connecting nodes results in a {6 5 .8} cds net. For a comparison with the coordinating abilities of the previously reported 1,4-bis( n octoxy)-2,5-bis(4,2':6',4''-terpyridin-4'-yl)benzene ( 3 ), a more flexible analogue 9 was prepared. {[Co(NCS) 2 ( 9 )]∙2CHCl 3 } n contains a (4,4) net defined by both metal and ligand planar 4-connecting nodes. The n octoxy tails of 9 protrude from each side of the (4,4) net and thread through adjacent sheets; the arene-attached n octoxy chains associate through a combination of van der Waals and C–H...π interaction