{5,10,15,20-Tetra-kis[4-(hex-yloxy)phen-yl]porphyrinato}nickel(II).

The mol-ecule of the title compound, [Ni(C(68)H(76)N(4)O(4))], is located on a crystallographic inversion center. The Ni-N distances within the square-shaped coordination environment are 1.951 (2) and 1.954 (2) Å. Three terminal C atoms in one of the hexyl groups are disordered over two sets of sites, with site-occupancy factors of 0.615 (13) and 0.385 (13).

{5,10,15,20-Tetra-kis[4-(oct-yloxy)phen-yl]porphyrinato}copper(II).

In the title compound, [Cu(C(76)H(92)N(4)O(4))], the central Cu(II) ion is situated on an inversion centre. The porphyrinate core exhibits a nearly planar conformation [maximum deviation = 0.027 (3) Å], with Cu-N distances of 1.997 (2) and 2.001 (2) Å. The benzene rings of the 4-octyloxyphenyl groups are rotated at angles of 84.02 (8) and 77.02 (6)° with respect to the mean plane of the porphyrin fragment. The two terminal C atoms in the octyl group are disordered over two positions of equal occupancy.

{meso-Tetra-kis[p-(hept-yloxy)phen-yl]-porphyrinato}silver(II).

The title compound, [Ag(C(72)H(84)N(4)O(4))], crystallizes with the Ag(II) cation on a centre of symmetry. The macrocyclic 24-membered ring core is planar with a mean deviation of 0.0311 (15) Šand the four-coordinate Ag(II) cation fits into its center, at 2.0814 (19) and 2.0872 (19) Å, from the surrounding pyrrole-N atoms, in agreement with what is found in related compounds. The p-heptyl-oxyphenyl groups are rotated 75.51 (5) and 84.45 (8)° with respect to the porphyrin mean plane, due to steric hindrance with the pyrrole-H atoms of the macrocycle.

[(1,3-Benzothia-zol-2-yl)amino-carbon-yl]meth-yl piperidine-1-carbodithio-ate monohydrate.

In the title compound, C(15)H(17)N(3)OS(3)·H(2)O, the piperidine ring has a chair conformation. The crystal structure is stabilized by weak inter-molecular N-H⋯O, O-H⋯N and O-H⋯O hydrogen-bonding inter-actions.

[meso-Tetra-kis(4-heptyl-oxyphen-yl)porphyrinato]nickel(II).

In the title compound, [Ni(C(72)H(84)N(4)O(4))], the four-coordinate Ni(II) ion in the middle of the planar 24-membered porphyrin ring is located on a crystallograpic inversion center, with Ni-N distances of 1.946 (2)-1.951 (2) Å. The 4-heptyl-oxyphenyl groups are twisted with respect to the porphyrin mean plane, the dihedral angles being 88.5 (3) and 79.1 (2)°.

Charge-transfer effect at the interface of phthalocyanine-electrode contact studied by scanning tunneling spectroscopy.

Scanning tunneling microscopy (STM) and spectroscopy (STS) are used in this work to investigate the charge-transfer effect at the molecule-substrate interface of substituted metal phthalocyanines. STS results revealed that the apparent energy gaps for both fluorinated phthalocyanines and unsubstituted phthalocyanines are essentially the same, which agree with the hybrid density functional calculations. More interestingly, there is a systematic shift of the energy level of valence bands, possibly as the result of charge-transfer effect at the molecule-substrate interface.