A Solid-State Spectral Effect in Eclipsed Tetracyanonickelates:  X-ray Crystal Structure, Polarized Specular Reflectance Spectroscopy, and ZINDO Modeling of Sr[Ni(CN)4]·5H2O, Rb2[Ni(CN)4]·H2O, and Na2[Ni(CN)4]·3H2O

Fronczek, Frank R.; Delord, Terry J.; Watkins, Steven F.; Gueorguieva, Petia G.; Stanley, George G.; Zizza, A; Cornelius, Jeffrey B.; Mantz, Yves A.; Musselman, Ronald L.

doi:10.1021/ic0345222

Cited by 4 publications

(7 citation statements)

References 45 publications

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“…The relative orientations of the molecules differs from plan to ruf as shown in Figure and discussed in an earlier section. The proximity of the planes (∼3.5 Å) leads one to suspect some perceptible degree of electronic and thus spectral perturbation; when Ni atoms are this close in Ni(CN) 4 2- salts, the 8000 cm -1 red-shifts mentioned earlier occur. ,, The Ni atoms in NiOEP, though, are 4.80 Å apart in the triclinic B form and 8.23 Å apart in the tetragonal form so we expect no metal−metal interaction. From Figure , one might expect, however, metal−pyrrole ring interaction in the triclinic B ( plan ) form and pyrrole−pyrrole interaction in the tetragonal ( ruf ) form.…”

Section: Calculations and Discussionmentioning

confidence: 79%

“…This small degree of overlap seems to be reflected in the small separation of energies from monomer to dimer orbitals as shown in Figure . Metal−pyrrole π interaction was suspected in the triclinic B form, and the metal orbitals most likely to interact with orbitals on neighboring molecules are the p z and d z 2 orbitals which were found to form extended lobes along metal chains in Ni(CN) 4 2- salts. , We see no such orbital overlap between molecules in Figure S4. In addition to intrinsic features of dimer MO's, we are interested in the origins of dimer MO's so we may assign dimer transitions as derivatives of the monomer, or standard molecular, assigned transitions such as those for Q or B.…”

Section: Calculations and Discussionmentioning

confidence: 83%

“…Nickel atoms on one plane lie over an edge of the pyrrole ring of an adjacent plane. Such relatively close stacking has resulted in significant red-shifting from solution values of transitions involving Ni p and d orbitals in tetracyanonickelate salts, and this effect has been also observed in the ZINDO modeling of those systems. , …”

Section: Methodsmentioning

confidence: 78%

“…(Recall, for instance, that the experimental plan − ruf red shift is 2490 cm -1 and the calculated value for monomers is 870 cm -1 .) We have been successful in modeling solid-state transitions in Ni(CN) 4 2- salts using ZINDO on both dimers and trimers in the actual crystal configuration. , In the case of Sr[Ni(CN) 4 )], we found that a trimer calculation can reproduce 87% of the experimental solution-to-solid-state red-shift and even a dimer can produce 47% of the trimer's perturbation …”

Section: Calculations and Discussionmentioning

confidence: 96%

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Red Shifting Due to Nonplanarity in Alkylporphyrins: Solid-State Polarized UV−Vis Spectra and ZINDO Calculations of Two Nickel(II)octaethylporphyrins

Evans

Musselman

2004

Inorg. Chem.

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We present the first demonstration of red shifting upon nonplanarity in alkylporphyrins using two pure conformations having known structures with identical substituents. The traditional view about the relationship of spectral red shifting to nonplanar deformation in porphyrins has been that the deformation from planar to nonplanar forms is in itself the cause of the shifting, but recently this view has been challenged. Among the new arguments is that the substituents required to effect conformational change also bring about nuclear rearrangements in the porphyrin complex which is the actual cause of the red shifting. Octaethylporphyrinatonickel(II), however, exists in both planar and ruffled forms which are determined only by the crystal structure, thus making the issue of different substituents moot. Using a polarized specular reflectance UV-vis microspectrophotometer, we have obtained polarized spectra of pure, solid samples of both forms of NiOEP. We find Soret band red shifting in the solid state that is much larger than previous reports of solution spectra and also report Q-band red shifting. We performed ZINDO calculations on monomers and dimers of both forms of NiOEP, based upon reported structures, and have reproduced the reported solution transition energies and our solid-state spectra as well as the red shifts that we and others have found experimentally. We conclude that, at least in this system, red shifting does indeed result primarily from conformation changes in the porphyrin.

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Section: Calculations and Discussionmentioning

confidence: 79%

Section: Calculations and Discussionmentioning

confidence: 83%

Section: Methodsmentioning

confidence: 78%

Section: Calculations and Discussionmentioning

confidence: 96%

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Red Shifting Due to Nonplanarity in Alkylporphyrins: Solid-State Polarized UV−Vis Spectra and ZINDO Calculations of Two Nickel(II)octaethylporphyrins

Evans

Musselman

2004

Inorg. Chem.

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“…An optical conductivity spectrum, which describes the imaginary part of the dielectric constant e 2 , was obtained using the Kramers-Kronig transformation on the reflection data. [19] In Figure 6 a, intense bands were observed at 3.02 and 4.27 eV, which were attributed to an IVCT (Pt II !Pt IV ) band and an LMCT (bridging Br!Pt IV ) band, respectively. [4b] After transformation, the obtained optical conductivity spectrum afforded the corresponding E CT values, but the maximum was broad with a spectral width greater than 100 meV.…”

Section: Resultsmentioning

confidence: 99%

Observation of the Properties of a Single Unit of a Limited CDW Structure in a Pt^II/Pt^IV Host–Guest Binary System Based on a Square‐Shaped Complex

Hirahara

Takaishi

Yamashita

2009

Chemistry An Asian Journal

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A macrocyclic tetranuclear platinum(II) complex [Pt(en)(4,4'-bpy)](4)(NO(3))(8) (1(NO(3))(8); en = ethylenediamine, 4,4'-bpy = 4,4'-bipyridine) and a mononuclear platinum(IV) complex [Pt(en)(2)Br(2)]Br(2) (2Br(2)) formed two kinds of Pt(II)/Pt(IV) mixed valence assemblies when reacted: a discrete host-guest complex 12Br(10) (3) and an extended 1-D zigzag sheet 1(2)(3)Br(8)(NO(3))(6) (4). Single crystal X-ray analysis showed that the dimensions of the assemblies could be stoichiometrically controlled. Resonance Raman spectra suggested the presence of an intervalence interaction, which is typically observed for quasi-1-D halogen-bridged M(II)/M(IV) complexes. The intervalence interaction indicates the presence of an isolated {Pt(II)X-Pt(IV)-XPt(II)} moiety in the structure of 4. On the basis of electronic spectra and polarized reflectance measurements, we conclude that 4 exhibits intervalence charge transfer (IVCT) bands. A Kramers-Kronig transformation was carried out to obtain an optical conductivity spectrum, and two sub-bands corresponding to slightly different Pt(II)-Pt(IV) distances were observed.

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Molecular Deformation, Charge Flow, and Spongelike Behavior in Anion–π {[M(CN)₄]²⁻;[HAT(CN)₆]}_∞ (M=Ni, Pd, Pt) Supramolecular Stacks

Kuzniak-Glanowska

Pinkowicz

Hooper

et al. 2018

Chemistry A European J

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The synthesis, crystal structures, spectroscopic characterization, and comprehensive quantum-chemical calculations for a novel series of anion-π hybrid salts (XPh ) [M(CN) ][HAT(CN) ]⋅3 MeCN (X=P, M=Ni (1), Pd (3), Pt (5); X=As, M=Ni (2), Pd (4), Pt (6); HAT(CN) =1,4,5,8,9,11-hexaazatriphenylenehexacarbonitrile) are presented. The systems comprise 1D {[M(CN) ] ;[HAT(CN) ]} stacks, in which the electron-rich metal complexes adjust their orientation to match the electron-deficient areas of HAT(CN) . Electronic charge-transfer interactions along the stacks result in polarization of electron density within HAT(CN) and in perturbations along the {[M(CN) ] ;[HAT(CN) ]} contacts. Electronic structure analysis suggests, for example, a relocation of 0.1-0.2 e per molecule from [M(CN) ] to HAT(CN) and anion-π interaction energies of around -65 kcal mol . A reversible structural single-crystal-to-single-crystal transformation, through desolvation/resolvation processes in the solid state, is also reported and a scheme for the formation of anion-π [M(CN) ] /HAT(CN) adducts in MeCN is proposed.

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A Solid-State Spectral Effect in Eclipsed Tetracyanonickelates: X-ray Crystal Structure, Polarized Specular Reflectance Spectroscopy, and ZINDO Modeling of Sr[Ni(CN)₄]·5H₂O, Rb₂[Ni(CN)₄]·H₂O, and Na₂[Ni(CN)₄]·3H₂O

Cited by 4 publications

References 45 publications

Red Shifting Due to Nonplanarity in Alkylporphyrins: Solid-State Polarized UV−Vis Spectra and ZINDO Calculations of Two Nickel(II)octaethylporphyrins

Red Shifting Due to Nonplanarity in Alkylporphyrins: Solid-State Polarized UV−Vis Spectra and ZINDO Calculations of Two Nickel(II)octaethylporphyrins

Observation of the Properties of a Single Unit of a Limited CDW Structure in a Pt^II/Pt^IV Host–Guest Binary System Based on a Square‐Shaped Complex

Molecular Deformation, Charge Flow, and Spongelike Behavior in Anion–π {[M(CN)₄]²⁻;[HAT(CN)₆]}_∞ (M=Ni, Pd, Pt) Supramolecular Stacks

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A Solid-State Spectral Effect in Eclipsed Tetracyanonickelates: X-ray Crystal Structure, Polarized Specular Reflectance Spectroscopy, and ZINDO Modeling of Sr[Ni(CN)4]·5H2O, Rb2[Ni(CN)4]·H2O, and Na2[Ni(CN)4]·3H2O

Cited by 4 publications

References 45 publications

Red Shifting Due to Nonplanarity in Alkylporphyrins: Solid-State Polarized UV−Vis Spectra and ZINDO Calculations of Two Nickel(II)octaethylporphyrins

Red Shifting Due to Nonplanarity in Alkylporphyrins: Solid-State Polarized UV−Vis Spectra and ZINDO Calculations of Two Nickel(II)octaethylporphyrins

Observation of the Properties of a Single Unit of a Limited CDW Structure in a PtII/PtIV Host–Guest Binary System Based on a Square‐Shaped Complex

Molecular Deformation, Charge Flow, and Spongelike Behavior in Anion–π {[M(CN)4]2−;[HAT(CN)6]}∞ (M=Ni, Pd, Pt) Supramolecular Stacks

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About

A Solid-State Spectral Effect in Eclipsed Tetracyanonickelates: X-ray Crystal Structure, Polarized Specular Reflectance Spectroscopy, and ZINDO Modeling of Sr[Ni(CN)₄]·5H₂O, Rb₂[Ni(CN)₄]·H₂O, and Na₂[Ni(CN)₄]·3H₂O

Observation of the Properties of a Single Unit of a Limited CDW Structure in a Pt^II/Pt^IV Host–Guest Binary System Based on a Square‐Shaped Complex

Molecular Deformation, Charge Flow, and Spongelike Behavior in Anion–π {[M(CN)₄]²⁻;[HAT(CN)₆]}_∞ (M=Ni, Pd, Pt) Supramolecular Stacks