TY  - JOUR
AU  - Siemeling, Ulrich
AU  - Schirrmacher, Christian
AU  - Glebe, Ulrich
AU  - Bruhn, Clemens
AU  - Baio, Joe E.
AU  - Árnadóttir, Líney
AU  - Castner, David G.
AU  - Weidner, Tobias
T1  - Phthalocyaninato complexes with peripheral alkylthio chains: Disk-like adsorbate species for the vertical anchoring of ligands onto gold surfaces
JO  - Inorganica Chimica Acta
PY  - 2011/
VL  - 374
IS  - 1
SP  - 302 
EP  -  312
UR  - http://www.sciencedirect.com/science/article/pii/S002016931100209X
DO  - 10.1016/j.ica.2011.02.048
KW  - structures
KW  - XPS
KW  - complexes
KW  - monolayer
KW  - NEXAFS
KW  - Self-assembled
KW  - spectroscopy
KW  - Thioether
KW  - crystal
KW  - X-ray
KW  - Phthalocyaninato
L1  - 
SN  - 
N1  - 
N1  - 
AB  - Thin metalorganic films were prepared on gold by self-assembly of thioether-functionalised phthalocyaninato complexes from solution. The phthalocyaninato ligands used contain eight peripheral, [beta]-positioned, alkylthio substituents SR (1a: R = n-C8H17, 1b: R = n-C12H25), which serve as headgroups for surface binding and promote lateral assembly, while the disk-like phthalocyaninato core offers the scope for the attachment of axial ligands to the adsorbed molecules. This process was mimicked by coordination of pyridine (Py) to [Zn(1a)] and [Zn(1b)], respectively. The crystal structures of the products [Zn(1a)(Py)] and [Zn(1b)(Py)] were determined. The crystal structures of 4,5-bis(octylthio)phthalodinitrile and 4,5-bis(dodecylthio)phthalodinitrile were also determined. The films fabricated from [Mn(1a)Cl] and [Mn(1b)Cl] on gold were characterised by XPS, ToF-SIMS and NEXAFS spectroscopy, which revealed the presence of well-defined and homogeneous self-assembled monolayers (SAMs), whose constituents are bound to the substrate by thioether-gold linkages. The orientation of the macrocycles is predominantly parallel to the surface. Strong electronic interaction of the manganese(III) centre with the substrate leads to Cl loss upon adsorption and its reduction to MnII.
ER  -