Reactions of nitric oxide with cobalt(II) tetraphenylporphyrin: a unique bis nitric oxide complex

Wayland, Bradford B.; Minkiewicz, J. V.

doi:10.1039/c39760001015

Cited by 11 publications

(13 citation statements)

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“…The spin of these square-planar complexes has been investigated with respect to the substrate-molecular bonding and the competitive axial ligation with NO. In the free molecules, the low-spin (S ¼ 1/2), 9 intermediate-spin (S ¼ 1) 32 and high-spin (S ¼ 5/2) 33 states of CoTPP, FeTPP and MnTPP, respectively, were reconfigured to low-spin (S ¼ 0, 1/2, 0) 9,[34][35][36] upon NO (S ¼ 1/2) coordination. As a basis for the discussion of the on-surface coordination in the focus of this paper, molecular orbital (MO) diagrams 37 illustrating the NO binding in the absence of the surface-ligand are provided (Fig.…”

Section: Methodsmentioning

confidence: 99%

On-surface coordination chemistry of planar molecular spin systems: novel magnetochemical effects induced by axial ligands

et al. 2012

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Paramagnetic transition-metal complexes assembled on surfaces are of great interest for potential applications in organic spintronics. The magnetochemical interactions of the spin of the metal centers with both ferromagnetic surfaces and optional axial ligands are yet to be understood. We use a combination of X-ray magnetic circular dichroism (XMCD) and quantum-chemical simulations based on density functional theory (DFT+U) to investigate these metal-organic interfaces with chemically tunable magnetization. The interplay between an optional axial ligand (NO, spin S=1/2 or NH 3 , S=0) and Ni and Co ferromagnetic surfaces affecting the spin of Co(II) tetraphenylporphyrin (d 7 , S=1/2), Fe(II) tetraphenylporphyrin (d 6 , S=1), Mn(II) tetraphenylporphyrin (d 5 , S=5/2) and Mn(II) phthalocyanine (d 5 , S=3/2) is studied. We find that the structural trans effect on the surface rules the molecular spin state as well as the sign and strength of the exchange interaction with the substrate. We refer to this observation as the surface spin-trans effect.

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Section: Methodsmentioning

confidence: 99%

On-surface coordination chemistry of planar molecular spin systems: novel magnetochemical effects induced by axial ligands

et al. 2012

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“…The bias dependent images taken at room-temperature reveal the conformational flexibility of the NO ligand via the Co-N axis which provides an indirect confirmation for the bending of the ligand expected from coordination chemistry and for its temperature activated rotation. 13,14 We also find that the CoTPP ad-molecules in the second layer are remarkably stable and can be imaged individually. Interestingly the second layer molecules possess a lower (two-fold) symmetry -however only after NO-ligation.…”

Section: Discussionmentioning

confidence: 59%

“…12,6 The bias dependent roomtemperature images reveal the conformational flexibility of the NO ligand which provides an indirect confirmation for a bent Co-NO bond. 13,14 Interestingly, the CoTPP ad-molecules observed in the second layer posses a lowered (2-fold) symmerty -however only after NO-ligation. Remarkably the present scanning tunneling microscopy study allows for the analysis of complex on-surface coordination reactions and monitors conformational and structural issues -even in dependence of first vs. second layer position of the molecules.…”

Section: Discussionmentioning

confidence: 99%

“…45 with NO (one unpaired electron in π*) has been studied in bulk / solution 13,14 as well as in the on-surface environment. 5,7,8,12 12,15 In our study, the CoTPP-nitrosyl complexes are imaged at roomtemperature, in contrast.…”

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confidence: 99%

“…We focus here on the chemical ligation of the molecular adsorbate on the basis of STM data, while in earlier studies we reported on the modification of the magnetic moment in CoTPP induced by a ferromagnetic substrate. The axial ligation of CoTPP with NO has been studied in bulk crystals and in the solution 13,14 as well as in the on-surface environment. 5,7,8,12 For the s-type overlap between the d z 2 orbital of Co and the p* of NO, molecular orbital (MO) theory predicts a B1201 Co-NO bond-angle.…”

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On-surface coordination chemistry: direct imaging of the conformational freedom of an axial ligand at room temperature

Wäckerlin

Siewert

Jung

et al. 2013

Phys. Chem. Chem. Phys.

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The on-surface ligation of nitric oxide (NO) with Co-tetraphenylporphyrin (CoTPP) sublimed onto oxygen-reconstructed Ni(001) is studied using room-temperature scanning tunneling microscopy (STM) and complementary photoemission spectroscopies. On the oxygen-reconstructed substrates, the porphyrins are observed to form well-ordered, self-assembled layers. STM directly images the NO ligand as a characteristic feature in the center of the molecule. Under certain STM imaging conditions the dynamicity of this feature can be related to the temperature-activated conformational flexibility of the NO ligand. This provides an indirect confirmation of the bending of the Co-NO bond, as predicted from classical coordination chemistry.

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Bis Axial Ligation of Simple Imine and Methyleneamido Groups by Ruthenium Porphyrins

Huang

Leung

Cheung

et al. 2000

Chemistry A European J

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Bis(N-ethylideneethanamine)ruthenium(ii) porphyrins, [Ru11(Por)(N(Et)=CHMe)2] (Por=TTP, 4-Cl-TPP), were prepared by the reaction of dioxoruthenium(VI) porphyrins with triethylamine in approximately 85% yields. The reaction between dioxoruthenium(VI) porphyrins and benzophenone imine afforded bis(diphenylmethyleneamido)ruthenium(IV) porphyrins, [Ru(IV)(Por)(N=CPh2)2] (Por=TTP, 3,4,5-MeO-TPP), in approximately 65% yields. These new classes of metalloporphyrins were characterized by 1H NMR, UV/Vis, and IR spectroscopy as well as by mass spectrometry and elemental analysis. The X-ray crystallographic structures of [Ru(II)(TTP)(N(Et)=CHMe)2] and [Ru(IV)(3,4,5-MeO-TPP)(N=CPh2)2] revealed an axial Ru-N bond length of 2.115(6) A for the imine complex and 1.896(8) A for the methyleneamido complex. Each of the N=CPh2 axial groups in [Ru(IV)(3,4,5-MeO-TPP)(N=CPh2)2] adopts a linear coordination mode with a corresponding Ru-N-C angle of 175.9(9)degrees. Spectral and structural studies revealed essentially single bonding character for the bis(imine) complexes but a multiple bonding character for the bis(methyleneamido) complexes with respect to their axial Ru-N bonds.

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Reactions of nitric oxide with cobalt(II) tetraphenylporphyrin: a unique bis nitric oxide complex

Cited by 11 publications

References 0 publications

On-surface coordination chemistry of planar molecular spin systems: novel magnetochemical effects induced by axial ligands

On-surface coordination chemistry of planar molecular spin systems: novel magnetochemical effects induced by axial ligands

On-surface coordination chemistry: direct imaging of the conformational freedom of an axial ligand at room temperature

Bis Axial Ligation of Simple Imine and Methyleneamido Groups by Ruthenium Porphyrins

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