Density Functional Theory Prediction of the Electrocatalytic Mechanism of Proton Reduction by a Dicobalt Tetrakis(Schiff Base) Macrocycle.

A dicobalt tetrakis(Schiff base) macrocycle has recently been reported to electrochemically catalyze the reduction of H+ to H2 in an acetonitrile solution. Density functional theory (DFT) calculations using the ωB97X-D functional are shown to produce structural and thermodynamic results in good agreement with the experimental data. A mechanistic model based on thermodynamics is developed that incorporates electrochemical and magnetic details of the complex, accounting for electron-spin reorganization of the metal center after redox steps. The model is validated through a comparison of the predicted electrochemical potentials with the irreversible cyclic voltammogram of [Co2LAc]+, which shows redox-coupled spin-crossover (RCSCO) behavior for the CoII/III transitions. Using our model, we predict the thermodynamically favored mechanism of H2 evolution by [Co2L]2+ to be one of heterolytic proton attack on a [CoII2L(µ-H)]+ species. Understanding the electronic details and thermodynamically preferred mechanism of this catalyst will aid in improving its efficiency and the future design of bimetallic Co-based H+ electrocatalysts. Also, this work will assist in the future DFT modeling of bimetallic RCSCO complexes.

Electrochemical Rectification of Redox Mediators Using Porphyrin-Based Molecular Multilayered Films on ITO Electrodes.

Electrochemical charge transfer through multilayer thin films of zinc and nickel 5,10,15,20-tetra(4-ethynylphenyl) porphyrin constructed via copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) "click" chemistry was examined. Current rectification toward various outer-sphere redox probes is revealed with increasing numbers of layers, as these films possess insulating properties over the neutral potential range of the porphyrin, then become conductive upon reaching its oxidation potential. Interfacial electron transfer rates of mediator-dye interactions toward [Co(bpy)3](2+), [Co(dmb)3](2+), [Co(NO2-phen)3](2+), [Fe(bpy)3](2+), and ferrocene (Fc), all outer-sphere redox species, were measured by hydrodynamic methods. The ability to modify electroactive films' interfacial electron transfer rates, as well as current rectification toward redox species, has broad applicability in a number of devices, particularly photovoltaics and photogalvanics.

Temperature-dependent and bistable current-voltage measurements in zinc porphyrin molecular junctions.

We report bistability in current-voltage curves from di(PEP)PorZn in an electromigrated molecular junction. Bistability was observed at ±0.3 V at 300 K but did not occur at 4 K. No bistability was identified at 300 K for another porphyrin molecule (di(Xyl)PorZn), where the phenyl-ethnyl-phenyl (PEP) side groups were replaced with a flexible p-xylene. Molecular dynamics simulations show that bistability may be due to conformation changes related to the fluctuation of the dihedral angle surrounding the zinc and/or the rotation of the porphyrin central plane of the molecule. Results suggest that other mechanisms may play a role in the current-voltage characteristics observed.

Synthesis, Characterization, and Fluorescence Properties of Mixed Molecular Multilayer Films of BODIPY and Zn(II) Tetraphenylporphyrins.

A new azido functionalized 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) has been synthesized to achieve spectral complementarity to a Zn(II) tetraphenylethynyl porphyrin (ZnTPEP). Mixed multilayer films were assembled on glass and quartz up to 10 bilayers thick in a layer-by-layer (LbL) fabrication process using copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) to couple these two dyes together with a tris-azido linker. By varying the amount of BODIPY in the CuAAC reaction solutions for the azido linker layers, we achieve tunable doping of BODIPY within the porphyrin films. We are able to demonstrate linear film growth and determine thickness by X-ray reflectivity (XRR). XRR data indicated that lower BODIPY loading leads to higher porphyrin content and slightly thicker films. Fluorescence emission and excitation spectra of the mixed multilayer films show efficient quenching of the BODIPY singlet and enhanced ZnTPEP emission, suggesting efficient energy transfer (EnT). The ease of fabrication and tunability of these films may serve as potential light harvesting arrays for molecular-based solar cells.

Electrocatalytic proton reduction by a dicobalt tetrakis-Schiff base macrocycle in nonaqueous electrolyte.

A series of dicobalt complexes, Co2L(2+) and Co2LAc(+), where L is a N6O2 coordinating bis(phenolate) tetrakis-Schiff base ligand, have been synthesized and characterized via electrochemical and spectroscopic techniques. [Co2LAc](ClO4) crystallizes in the monoclinic space group P21/n, and the structure reveals a highly distorted octahedral geometry for the Co(II) ions, which are bridged by an acetate with a Co-Co distance of 3.2 Å. Cyclic voltammetry (CV) of Co2L(2+) and Co2LAc(+) in anhydrous acetonitrile reveals large anodic/cathodic peak splitting for the Co(II/III) redox transitions and a multielectron wave for the Co(II/I) reductions. The CVs for Co2L(2+) and Co2LAc(+) were also compared to those of Zn2LAc(+) and H4L(2+) to identify the ligand-center oxidations and reductions. Addition of trifluoroacetic acid (TFA) or acetic acid (AcOH) to the electrolyte solutions of Co2L(2+) results in an irreversible reduction wave that is consistent with electrocatalytic H(+) reduction. The catalytic rate law shows a first order dependence on [catalyst] and a second order dependence on [acid]. Using TFA as the acid source, the electrocatalytic H(+) reduction rate constant for Co2L(2+) was determined to be 138 M(-2) s(-1), while coordination of acetate slows the rate to 63 M(-2) s(-1) for Co2LAc(+). Controlled potential electrolysis of Co2L(2+) with AcOH generated H2 in 72-94% Faradaic efficiency as determined by gas chromatography. Initial studies suggest Co(I)2 as the catalytically active form of the complex. These complexes represent a new class of Co-based electrocatalytic H(+) reduction catalysts that utilize a bimetallic active site.

Structural, electrochemical, and spectroscopic investigation of acetate bridged dinuclear tetrakis-Schiff base macrocycles of Mn and Zn.

The synthesis of Mn2LAc+, Zn2LAc+, and H4L2+ is described, where L is a tetrakis-Schiff base macrocycle formed using 4-tert-butyl-2,6-diformylphenol and 2,2'-diamino-N-methyldiethylamine resulting in an N6O2 coordination environment. In Mn2LAc+ and Zn2LAc+, the two metal centers are bridged by an acetate ligand. [Mn2LAc](ClO4)·(DMF)0.5, [Mn2LAc](ClO4)·(ACN)0.5, and [Zn2LAc](PF6) crystallized in the space group P2(1)/c, with nearly identical unit-cell dimensions and geometric structures. Electrochemical analysis of Zn2LAc+, and H4L2+ by cyclic voltammetry (CV) revealed two irreversible anodic waves that were assigned to oxidations of the phenolate ligands. CVs of Mn2LAc+ displayed two chemically reversible anodic waves corresponding to Mn(II/III) oxidations, followed by irreversible oxidations of the phenolate ligands. Interfacial electron transfer rates for the single electron oxidations from Mn2(II)LAc+ to Mn(II)Mn(III)LAc2+ to Mn2(III)LAc+ determined from digital simulation of the CVs were 0.6 and 1.1 × 10(­3) cm s(­1), respectively. The sluggish interfacial electron transfer rates observed in electrochemical scans of Mn2LAc+ are consistent with broken symmetry density functional theory electronic structure calculations (B3LYP/6-311G(2df)/6-311G(d,p)) that predict large structural rearrangements of the Mn coordination environment upon oxidation to Mn(III) with associated Jahn­Teller distortions. Titration of Mn2LAc+, Zn2LAc+, and H4L2+ with NOPF6 in acetonitrile allowed for the isolation and spectroscopic examination of higher oxidations and were consistent with electrochemical assignments. The electrochemical and spectroscopic analysis of these complexes will aid in future studies involving electrocatalytic processes with related dinuclear macrocycles.

Photocurrent enhancement by multilayered porphyrin sensitizers in a photoelectrochemical cell.

Multilayer Zn(II) tetraphenylporphyrin chromophores, assembled using copper-catalyzed azide-alkyne cycloaddition (CuAAC), provide a new sensitization scheme that could be useful in dye-sensitized solar cells (DSSCs). We report on the photoelectrochemical responses of multilayer films of Zn(II) 5,10,15,20-tetra(4-ethynylphenyl)porphyrin (1) assembled on planar ITO substrates operating as a p-type DSSC using three different redox mediators. The traditional I(-)/I3(-) redox couple results in the greatest short circuit current densities (JSC) but very low open circuit potentials (VOC). The use of cobalt sepulchrate ([Co(sep)](2+/3+)) and cobalt tris-bipyridine ([Co(bpy)3](2+/3+)) as redox mediators generates higher VOC values, but at the expense of lower photocurrents. These results highlight the inherent differences in the interactions between the redox mediator and Zn(II) tetraphenylporphyrin multilayer films. Increasing the porphyrin content through multilayer growth proved to be effective in increasing the performance of photoelectrochemical cells with all three redox mediators. Cells using I(-)/I3(-) reached maximum performance (power output) at five porphyrin layers, [Co(bpy)3](2+/3+) at five layers, and [Co(sep)](2+/3+) at three layers. For all mediators, JSC increases with the addition of porphyrin layers beyond a monolayer. However, JSC reaches a maximum value at a point greater than one layer after which it decreases, presumably due to exciton diffusion limitations and the insulating effects of the multilayer film. Similarly, all cells also reach a maximum VOC beyond one porphyrin layer. We show that porphyrin arrays assembled using newly developed CuAAC layer-by-layer growth may be useful as a multilayer sensitization scheme for use in photoelectrochemical cells.

Efficient Förster resonance energy transfer in 1,2,3-triazole linked BODIPY-Zn(II) meso-tetraphenylporphyrin donor-acceptor arrays.

Cu(I) catalyzed azide-alkyne cycloaddition (CuAAC) reactivity was successfully employed to synthesize three donor-acceptor energy transfer (EnT) arrays that contain one (Dyad), three (Tetrad) and four (Pentad) 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) donors connected to a Zn-tetraphenylporphyrin acceptor via 1,2,3-triazole linkages. The photophysical properties of the three arrays, along with individual donor and acceptor chromophores, were investigated by UV-vis absorption and emission spectroscopy, fluorescence lifetimes, and density functional theory (DFT) electronic structure modeling. Comparison of the UV-vis absorption spectra and frontier molecular orbitals from DFT calculations of the three arrays with ZnTPP, ZnTTrzlP, and Trzl-BODIPY shows that the electronic structure of the chromophores is essentially unperturbed by the 1,2,3-triazole linkage. Time-dependent DFT (TDDFT) calculations on the Dyad reproduce the absorption spectra in THF and show no evidence of excited state mixing of the donor and acceptor. The BODIPY singlet excited state emission is significantly quenched in all three arrays, consistent with EnT to the porphyrin core, with efficiencies of 95.8, 97.5, and 97.2% for the Dyad, Tetrad, and Pentad, respectively. Fluorescence excitation spectra of the three arrays, measured at the porphyrin emission, mirror the absorption profile of both the porphyrin and BODIPY chromophores and are consistent with the Förster resonance energy transfer (FRET) mechanism. Applying Förster theory to the spectroscopic data of the chromophores gives EnT efficiency estimates that are in close agreement with experimental values, suggesting that the through-space mechanism plays a dominant role in the three arrays.

Structural analysis of porphyrin multilayer films on ITO assembled using copper(I)-catalyzed azide-alkyne cycloaddition by ATR IR.

We report the use of grazing-angle attenuated total reflectance (GATR) IR and polarized UV-vis to determine the molecular structure of porphyrin based molecular multilayer films grown in a layer-by-layer (LbL) fashion using copper-catalyzed azide-alkyne cycloaddition (CuAAC). The molecular orientation and bonding motif present in multilayer films of this type could impact their photophysical and electrochemical properties as well as potential applications. Multilayer films of M(II) 5,10,15,20-tetra(4-ethynylphenyl)porphyrin (1 M = Zn, 2 M = Cu) and azido based linkers 3-5 were used to fabricate the films on ITO substrates. Electrochemically determined coverage of films containing 2 match the trends observed in the absorbance. GATR-IR spectral analysis of the films indicate that CuAAC reactivity is leading to 1,4-triazole linked multilayers with increasing porphyrin and linker IR characteristic peaks. Films grown using all azido-linkers (3-5) display an oscillating trend in azide IR intensity suggesting that the surface bound azido group reacts with 1 and that further layering can occur through additional reaction with linkers, regenerating the azide surface. Films containing linker 5 in particular show an overall increase in azide content suggesting that only two of the three available groups react during multilayer fabrication, causing an overall buildup of azide content in the film. Films of 1 with linker 3 and 5 showed an average porphyrin plane angle of 46.4° with respect to the substrate as determined by GATR FT-IR. Polarized UV-vis absorbance measurements correlate well with the growth angle calculated by IR. The orientation of the porphyrin plane within the multilayer structures suggests that the CuAAC-LbL process results in a film with a trans bonding motif.

Thickness, surface morphology, and optical properties of porphyrin multilayer thin films assembled on Si(100) using copper(I)-catalyzed azide-alkyne cycloaddition.

We report the structure, optical properties and surface morphology of Si(100) supported molecular multilayers resulting from a layer-by-layer (LbL) fabrication method utilizing copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC), also known as "click" chemistry. Molecular based multilayer films comprised of 5,10,15,20-tetra(4-ethynylphenyl)porphyrinzinc(II) (1) and either 1,3,5-tris(azidomethyl)benzene (2) or 4,4'-diazido-2,2'-stilbenedisulfonic acid disodium salt (3) as a linker layer, displayed linear growth properties up to 19 bilayers. With a high degree of linearity, specular X-ray reflectivity (XRR) measurements yield an average thickness of 1.87 nm/bilayer for multilayers of 1 and 2 and 2.41 nm/bilayer for multilayers of 1 and 3. Surface roughnesses as determined by XRR data fitting were found to increase with the number of layers and generally were around 12% of the film thickness. Tapping mode AFM measurements confirm the continuous nature of the thin films with roughness values slightly larger than those determined from XRR. Spectroscopic ellipsometry measurements utilizing a Cauchy model mirror the XRR data for multilayer growth but with a slightly higher thickness per bilayer. Modeling of the ellipsometric data over the full visible region using an oscillator model produces an absorption profile closely resembling that of a multilayer grown on silica glass. Comparing intramolecular distances from DFT modeling with experimental film thicknesses, the average molecular growth angles were estimated between 40° and 70° with respect to the substrate surface depending on the bonding configuration.

A versatile molecular layer-by-layer thin film fabrication technique utilizing copper(I)-catalyzed azide-alkyne cycloaddition.

We have developed a rapid and versatile layer-by-layer (LbL) thin film fabrication method using copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) or "click" chemistry in the construction of molecular multilayer assemblies. Multilayers containing synthetic porphyrins, perylene diimides, and mixtures of the two have been constructed in order to highlight the versatility of this method. Characterization of thin films using UV-vis absorption, water contact angle, and electrochemical techniques indicate that multilayer growth is consistent over tens of layers. Preliminary X-ray reflectivity measurements yield an average bilayer thickness of 2.47 nm for multilayers of 1 and 3 grown on glass. Polarized absorption measurements suggest that the dense thin films exhibit moderate ordering in their molecular structure with partial alignment with respect to the surface normal.

Active-site models of bacterial nitric oxide reductase featuring tris-histidyl and glutamic acid mimics: influence of a carboxylate ligand on Fe(B) binding and the heme Fe/Fe(B) redox potential.

Active-site models of bacterial nitric oxide reductase (NOR) featuring a heme Fe and a trisimidazole- and glutaric acid-bound non-heme Fe (Fe(B)) have been synthesized. These models closely replicate the proposed active site of native NORs. Examination of these models shows that the glutamic acid mimic is required for both Fe(B) retention in the distal binding site and proper modulation of the redox potentials of both the heme and non-heme Fe's.

A new class of mixed-valence systems with orbitally degenerate organic redox centers. Examples based on hexa-rhenium molecular prisms.

The ligand-centered mixed-valence (LCMV) properties of two supramolecular complexes are reported: triangular prisms of the form ([Re(CO)3]2X)3-mu,mu',mu' '-[tPyTz]2, where X is 2,2'-bisbenzimidazolate (1) or a pair of benzylthiols (2), and tPyTz is tri-(4-pyridyl)-1,3,5-triazine. Cyclic voltammetry demonstrates that the redox-accessible bridging ligands, tPyTz, are reduced in sequential, one-electron reactions. The singly reduced prisms, which represent an unusual type of mixed-valence compound in which the tPyTz ligands themselves are the redox centers, show intense, broad intervalance transfer (IT) bands in the NIR, consistent with highly coupled MV species. Electroabsorption (Stark spectroscopy) measurements reveal small dipole moment changes associated with intervalence excitation (|Deltamu12| = 0.30 +/- 0.02 eA for 1- and 0.48 +/- 0.02 eA for 2-), as well as noncollinear transition dipole moment (mu12) and dipole moment change vectors (zeta approximately 45 degrees ). DFT electronic structure calculations support this unusual result, along with a through-space electronic interaction mechanism. The neutral complexes (D3h symmetry) possess doubly degenerate, but spatially distinct, LUMO and LUMO+ orbitals. The orbital degeneracy of the tPyTz ligands is lifted in the MV forms, resulting in nonsymmetrical charge redistribution within the molecules upon on optical IT.

Underlying spin-orbit coupling structure of intervalence charge transfer bands in dinuclear polypyridyl complexes of ruthenium and osmium.

The mixed-valence systems meso- and rac-[{M(bpy)2}2(mu-BL)]5+ {M = Ru, Os; BL = a series of polypyridyl bridging ligands such as 2,3-bis(2-pyridyl)benzoquinoxaline (dpb)} are characterized by multiple intervalence charge transfer (IVCT) and interconfigurational (IC) bands in the mid-infrared and near-infrared (NIR) regions. Differences in the relative energies of the IC transitions for the fully oxidized (+6) states of the osmium systems demonstrate that stereochemical effects lead to fundamental changes in the energy levels of the metal-based dpi orbitals, which are split by spin-orbit coupling and ligand-field asymmetry. An increase in the separation between the IC bands as BL is varied reflects the increase in the degree of electronic coupling through the series of ruthenium and osmium complexes. The increase in the IVCT bandwidths for the former is therefore attributed to the increase in the separation of the three underlying components of the bands. Stark effect measurements reveal small dipole moment changes accompanying IVCT excitation in support of the localized-to-delocalized or delocalized classification for the dinuclear ruthenium and osmium systems.

Selective functionalization of independently addressed microelectrodes by electrochemical activation and deactivation of a coupling catalyst.

We demonstrate selective functionalization of independently addressed microelectrodes by electrochemical activation and deactivation of a coupling catalyst. 1,2,3-Triazole formation between terminal acetylenes and organic azides is efficiently catalyzed by copper(I) complexes (a Sharpless "click" reaction), while the oxidized copper(II) complexes are inactive. By electrochemically activating or deactivating the catalyst by switching its redox state, we demonstrate control over triazole formation between surface-immobilized azides and ethynylferrocene. The reaction proceeds on the time scale of minutes using submicromolar concentration of reactants and catalyst, requires mild potentials for catalyst activation and deactivation, and works in aqueous and mixed aqueous-organic solvents. By appropriate biasing of each electrode, we selectively modify one of two chemically identical 10-mum-wide electrodes separated by 10 mum in an interdigitated array. The ability to switch on or off the reaction by electrical addressing together with the chemoselectivity of this reaction makes Cu(I)-catalyzed triazole formation an ideal method for the chemical modification of multielectrode arrays.

Efficient synthesis of trisimidazole and glutaric acid bearing porphyrins: ligands for active-site models of bacterial nitric oxide reductase.

Ligands (1) for active-site models of bacterial nitric oxide reductase (NOR) have been efficiently synthesized. These compounds (1) feature three imidazolyl moieties and one carboxylic acid residue at the FeB site, which represent the closest available synthetic model ligands of NOR active center. The stereo conformations of these ligands are established on the basis of steric effects and 1H NMR chemical shifts under the ring current effect of the porphyrin.

C- and Z-shaped coordination compounds. synthesis, structure, and spectroelectrochemistry of cis- and trans-[Re(CO)3(L)]2-2,2'-bisbenzimidizolate with L = 4-phenylpyridine, 2,4'-bipyridine, or pyridine.

A series of C- and Z-shaped complexes of the form cis- and trans-[Re(CO)3(L)]2BiBzIm, where L = 4-phenylpyridine, 2,4'-bipyridine, or pyridine and BiBzIm = 2,2'-bisbenzimidizolate, have been synthesized by the reaction of [Re(CO)4]2BiBzIm with a slight excess of L in refluxing tetrahydrofuran. Five of the six compounds have been isolated and crystallographically and electrochemically characterized. Formation of the sixth, the cis form of the [Re(CO)3(4-phenylpyridine)]2BiBzIm, is evidently inhibited by the torsional steric demands of proximal 4-phenylpyridines. The compounds are acyclic analogues of recently studied tetrarhenium molecular rectangles and are of interest, in part, because of their potential to form ligand-centered mixed-valence (LCMV) compounds upon reduction by one electron. Spectroelectrochemical measurements corroborated the formation of a LCMV version of cis-[Re(CO)3(L)]2BiBzIm but failed to uncover a ligand-based intervalence transition. Electrochemical measurements revealed isomer-dependent L/L electrostatic effects, resulting in greater mixed-valence ion comproportionation for C-shaped assemblies versus Z-shaped assemblies.

Borderline class II/III ligand-centered mixed valency in a porphyrinic molecular rectangle.

A molecular rectangle of the form ([Re(CO)(3)](2)BiBzIm)(2)-mu,mu'-(LL)(2), where BiBzIm is 2,2'-bisbenzimidazolate and LL are cofacially aligned [5,15-bis(4-ethynylpyridyl)-10,20-bis(n-hexyl)-porphyrinato]zinc ligands, has been examined via electrochemical, spectroelectrochemical, and electronic Stark effect methods. The rectangle displays three electrochemically accessible reductions assigned as LL based. The singly reduced rectangles are part of an unusual class of mixed-valence complexes where cofacial ligands, in this case porphyrins, comprise the degenerate redox centers. Absorption spectra for the singly reduced rectangle show two intense and narrow absorption bands in the near-infrared (NIR) region; the lower energy band is assigned as an intervalence transition. Time-dependent density functional theory electronic structure calculations support the assignment. Curiously, the transition displays a non-Marcus-type solvent dependence. NIR region electroabsorbance measurements of the singly reduced rectangle reveal a small but readily measurable dipole moment change of 0.56 +/- 0.05 eA. On the basis of spectroelectrochemical and electroabsorption measurements, the singly reduced rectangle is assigned as a borderline class II/class III mixed-valence species.

Tetra-rhenium molecular rectangles as organizational motifs for the investigation of ligand-centered mixed valency: three examples of full delocalization.

Molecular rectangles having the form ([Re(CO)3]2(X)2)(2)-mu,mu'-(LL)2, where X is either a bridging alkoxide or phenylthiolate group and LL is 4,4'-bipyridine or pyrazine, are characterized by cofacial LL pairs that are in van der Waals contact across the "long" side of the rectangle. Cyclic voltammetry shows that the redox-accessible bridging ligands, LL, are reduced in sequential, one-electron reactions. The singly reduced rectangles represent an unusual type of mixed-valence compound in which the LL ligands themselves are the redox centers. Spectroelectrochemical measurements for mixed-valence forms of these rectangles reveal intense, asymmetric absorption bands in the near-infrared region, assigned as intervalence transitions. Electroabsorption (Stark spectroscopy) measurements reveal minute changes in dipole moment and therefore a lack of significant charge transfer upon intervalence excitation. Thus, the rectangles are unusual examples of class III (fully valence delocalized) molecular mixed-valence species that employ direct donor-orbital/acceptor-orbital overlap rather than covalent-bond-mediated superexchange to achieve the large electronic coupling strengths required for delocalization.

Rhenium-based molecular rectangles as frameworks for ligand-centered mixed valency and optical electron transfer.

A series of six neutral, tetrametallic, molecular rectangles has been synthesized that have the form ([Re(CO)(3)](2)BiBzIm)(2)-mu,mu'-(LL)(2), where BiBzIm is 2,2'-bisbenzimidazolate and LL is a reducible, dipyridyl or diazine ligand. X-ray crystallographic studies of the six show that the rectangle frameworks, as defined by the metal atoms, range in size from 5.7 A x 7.2 A to 5.7 A x 19.8 A. The singly reduced rectangles are members of an unusual category of mixed-valence compounds in which the ligands themselves are the redox centers and interligand electronic communication is controlled by direct ligand orbital overlap rather than by superexchange through the metal ions. Despite nominally identical coordination-defined ligand positioning, the spectrally determined electronic strengths, H(ab)2, vary by roughly 100-fold. As shown by X-ray crystallography and computational modeling, the observed differences largely reflect detailed geometric configurational differences that can either facilitate or frustrate productive direct orbital overlap.