Synthesis and conductivities of (μ-cyano)phthalocyaninatometal compounds

Metallomacrocycle (MacM) complex with cyanide as bridged ligand: Electronic structures of [MacMCN]n

“…We have summarized the results for the polymers studied including experimental measurements (conductivity and energy band gap) 37–47 in Table V. The metallomacrocycle polymers with cyano‐bridged ligand showed semiconducting properties, with a similar tendency as the experimental measurements of conductivity and band gap.…”

“…The introduction of an axial ligand CN − modifies the ground‐state electronic configuration of metallomacrocycles described in the previous section. Experimental evidence confirm that the central metal atom shows an oxidation state +III in [MacM(CN) 2 ] − complexes, as well as [MacMCN] n polymers 37–41. These compounds show an electron spin resonance (ESR) silent sign, associated to a restricted electronic state 45, 46.…”

“…Figure 1 shows the molecular stacking. The bridged structure shown in Figure 2 has been confirmed for many compounds using a variety of physical methods [infrared (IR), Mössbauer spectroscopy, nuclear magnetic resonance (NMR), thermogravimetry, and scanning tunneling microscopy] 37–46. The crystal structure of K[PcCo(CN) 2 ] is known and confirms the bisaxial coordination of the CN − groups.…”

“…We have first performed calculations on the isolated MacM [M=Co, Rh; Mac=phthalocyanine (Pc), tetrabenzoporphyrine (TBP)] molecules using the experimental geometry (X‐ray data) 37–41, with appropriate averaging of bond angles and bond lengths to maintain the D 4 h symmetry. The monomers have been built up by linking MacM (metallomacrocycle) with CN − , metal over ligand, along the stacking direction ( z axis in our coordinate system).…”

“…in the oxidation state +III. An appropriate bridging ligand may be a charged molecule such as cyanide (CN − ), which can generate the M′[MacM(CN) 2 ] complexes and [MacM(CN)] n polymers (M′=Na, K; Mac=Pc, TBP; M=Co, Rh, Fe, Mn, Cr) 37–44. All the cyano‐bridged macrocycle metal complexes show comparatively high powder conductivities.…”