(Tetramethylporphyrinato)nickel 7,7,8,8-tetracyanoquinodimethane, Ni(TMP)TCNQ. Synthesis, structure, and physical properties

Pace, Laurel J.; Ulman, Abraham; Ibers, James A.

doi:10.1021/ic00131a037

Cited by 44 publications

(23 citation statements)

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“…Examples in Table 2 are Ni(P), 26b the triclinic forms of Ni(OEP), 37,38 and Ni(TMP) (meso-tetramethylporphyrin). 39 The recently crystallized structure of Ni(P) is almost planar; however, closer examination of the macrocycle shows small but significant contributions from ruf and waV(y) deformations induced by packing forces. The nearly planar crystal structures of Ni(OEP) also exhibit both the waV(x) and waV(y) deformations.…”

Section: Resultsmentioning

confidence: 98%

“…The nearly planar crystal structures of Ni(OEP) also exhibit both the waV(x) and waV(y) deformations. Moreover, a crystal structure of Ni(TMP) 39 is significantly nonplanar; its nonplanar distortion is largely a combination of ruf and waV(x) with smaller contributions of sad and waV(y) deformations. For Ni(OEP) and Ni(TMP), both the crystal packing and the substituents probably account for the distortions.…”

Section: Resultsmentioning

confidence: 99%

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Structural Characterization of Synthetic and Protein-Bound Porphyrins in Terms of the Lowest-Frequency Normal Coordinates of the Macrocycle

1997

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The X-ray crystal structures of synthetic and protein-bound metalloporphyrins are analyzed using a new normal structural decomposition method for classifying and quantifying their out-of-plane and in-plane distortions. These distortions are characterized in terms of equivalent displacements along the normal coordinates of the D 4h -symmetric porphyrin macrocycle (normal deformations) by using a computational procedure developed for this purpose. Often it turns out that the macrocyclic structure is, even in highly distorted porphyrins, accurately represented by displacements along only the lowest-frequency normal coordinates. Accordingly, the macrocyclic structure obtained from just the out-of-plane normal deformations of the saddling (sad, B 2u )-, ruffling (ruf, B 1u )-, doming (dom, A 2u )-, waving [waV(x), waV(y); E g ]-, and propellering (pro, A 1u )-type essentially simulates the out-of-plane distortion of the X-ray crystal structure. Similarly, the observed inplane distortions are decomposed into in-plane normal deformations corresponding to the lowest-frequency vibrational modes including macrocycle stretching in the direction of the meso-carbon atoms (meso-str, B 2g ), stretching in the direction of the nitrogen atoms (N-str, B 1g ), x and y pyrrole translations [trn(x), trn(y); E u ], macrocycle breathing (bre, A 1g ), and pyrrole rotation (rot, A 2g ). The finding that the displacements of the 24 atoms of the macrocycle primarily occur along the lowest-frequency normal coordinates is expected on physical grounds and is verified by structural decomposition of more than 100 synthetic and 150 protein-bound metalloporphyrin X-ray crystal structures. Because of the high resolution of the X-ray crystal structures of synthetic metalloporphyrins, the small displacements for other normal coordinates are also able to be discerned. However, for the heme groups in proteins, only the displacements along the lowest-frequency modes are detectable because of the large uncertainties in the atomic positions. The heme groups in the four X-ray crystal structures of deoxyhemoglobin are used to evaluate the structural decomposition method. We find that the corresponding heme groups in different X-ray crystal structures are similar. Furthermore, the outof-plane distortions for the heme groups in the R-and -chains are found to be inequivalent, that is, the two

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Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Structural Characterization of Synthetic and Protein-Bound Porphyrins in Terms of the Lowest-Frequency Normal Coordinates of the Macrocycle

1997

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“…Daten der Kristallstrukturen folgender Verbindungen: Nickel(I1)-octaethylporphyrinat, tetragonale Form [IOa] (mittlerer (Ni-N)-Abstand 1,93 A), Nickel(II)-etioporphyrinat-I-bis(2,4,5,7-tetranitrofluorenon)-Komplex [23] (1,95 A), Nickel(II) -5,10, 15,20-tetramethylpo~hyrinat-7,7,8,8-tetracyanchinodimethan-Komplex [24] (1,95 A), zwei Nickel-tetrabenzoporphyrinat-Komplexe [26a] 4,19-cis-2,2,7,7,12,12,17,17-octamethyl-4,18,19,20-tetrahydrocorphinat (1,90 A) [27]; Nickel(I1) -4,6,19-cis-2,2,7,7,12,12-hexamethyl-6,15-dicyan-4,5,6,18,19,20-hexahydrocorphinat-isothiocyanat (2,09 A, paramagnetisch) [28] und entsprechendes 3,5-Dinitrobenzoat (2,08 A, paramagnetisch) [29]; Ni(1l)-Komplex 21 (1,93 A) [12], Ni(I1) -Komplex 22 (1,92 und 1,92 A) [13], Ni(I1)-Komplex 23 (1,91 A) [14], Ni(l1)-Komplex 24a(1,87 A) [15a], Ni(II) -Komplex24b(1,88 A) [15b]; fernerdie in Tub. 1 aufgefiihrten Ni(I1) -Komplexe 1 la, 10a, 12a, 4a, Sa, 2a, 15a und 16a, vgl.…”

Section: )unclassified

Die Sattelkonformation der hydroporphinoiden Nickel(II)‐Komplexe: Struktur, Ursprung und stereochemische Konsequenzen

Kratky¹,

Waditschatka²,

Angst³

et al. 1985

Helvetica Chimica Acta

136

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Thirteen crystal structures document the general phenomenon of coordination-hole contraction in hexahydro-and tetrahydroporphinoid ligands of complexes with small metal ions such as low-spin Ni(I1). The contraction is characterized by a deformation of the ligand system towards a saddle-shaped, ruMed conformation of approximate S, symmetry. The central metal ion is coplanar with the four coordinating N-centers whereas the four C(meso)-atoms arc situated alternately above and below this coordination plane. Increasing steepness of the saddle (parameter d,) is associated with decreasing metal-N distances. For metal pyrrocorphinates, d, increases in the order Cu(11) < (pyridine) Co(l1) < Ni(II), for Ni(1l) complexes it does so in the order porphyrin < chlorin ' ) ')Beziehbar von der Hauptbibliothek der ETH Zurich. Alle in dieser Arbeit vorkommenden chiralen Verbindungen waren in racemischer Form.

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“…TCNQ is one of several electron-deficient cyano compounds that form electron donor-acceptor (EDA) complexes with metalloporphyrins. [54][55][56][57][58][59] In fact, a number of EDA-stabilized liquid crystals are known, [60,61] including ferrimagnetically coupled columnar systems based on a Mn III porphyrin. [62,63] The adduct 1 b·nTCNQ was thus prepared.…”

Section: Phase Behavior Of Porphyrins 2 a Bmentioning

confidence: 99%

“…[55] When 1 b·nTCNQ is dissolved in CH 2 Cl 2 the CT band is no longer observed, indicating that the EDA interaction is not operative in solution.…”

mentioning

confidence: 99%

Discotic Liquid‐Crystalline Materials Based on Porphycenes: A Mesogenic Metalloporphycene–Tetracyanoquinodimethane (TCNQ) Adduct

Stępień

Donnio

Sessler

2007

Chemistry A European J

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A number of substituted zinc(II) porphycenes and porphyrins have been synthesized as potentially mesogenic materials. One of the resulting porphycenes, bearing eight decyloxy chains, exhibits two mesophases, a transient lamellar phase (Lam) and a highly ordered lamello-columnar phase (L(Col)), with remarkably different structural characteristics. The same zinc(II) porphycene also forms an electron donor-acceptor (EDA) complex with tetracyanoquinodimethane (TCNQ), generating a hexagonal columnar mesophase (Col(h)) that is thermally stable up to ca. 200 degrees C. The EDA interaction between porphycene and TCNQ has been probed using electronic and vibrational spectroscopy. A mixture of zinc(II) porphyrins, isomeric with the above porphycene complex, forms a rectangular columnar mesophase (Col(r)).

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(Tetramethylporphyrinato)nickel 7,7,8,8-tetracyanoquinodimethane, Ni(TMP)TCNQ. Synthesis, structure, and physical properties

Cited by 44 publications

References 1 publication

Structural Characterization of Synthetic and Protein-Bound Porphyrins in Terms of the Lowest-Frequency Normal Coordinates of the Macrocycle

Structural Characterization of Synthetic and Protein-Bound Porphyrins in Terms of the Lowest-Frequency Normal Coordinates of the Macrocycle

Die Sattelkonformation der hydroporphinoiden Nickel(II)‐Komplexe: Struktur, Ursprung und stereochemische Konsequenzen

Discotic Liquid‐Crystalline Materials Based on Porphycenes: A Mesogenic Metalloporphycene–Tetracyanoquinodimethane (TCNQ) Adduct

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