The project involves the design and synthesis of transition metal complexes and clusters with desired spectroscopic, electrochemical, and luminescence properties, and the investigation of the electronic structures of these complexes using theoretical studies. Computational studies, such as ab initio, Extended Hückel Molecular Orbital (EHMO), Density Functional Theory (DFT) calculations, on the newly synthesized metal complexes and clusters will be conducted. Correlation between the experimentally determined properties with the results obtained from theoretical studies will be pursued, which would serve as a means of providing insights into the structure, bonding and electronic structures of the complexes and clusters, and hence to the future design of this class of compounds with improved properties. These findings would also provide important insights into the future design and synthesis of novel molecular functional materials based on the utilization of these new metal complexes as building blocks.
The computational studies and molecular orbital calculations, such as ab initio, Extended Hückel Molecular Orbital (EHMO), Density Functional Theory (DFT) calculations, on the newly synthesized metal complexes and clusters would provide important insights into the understanding of the structure, bonding and electronic structures as well as spectroscopic and electrochemical properties of the metal complexes and clusters. These computational studies would serve as complementary tools and techniques towards the interpretation and understanding of the experimental findings, as well as the elucidation of molecular properties such as the spectroscopic and emission origin, electronic absorption and emission data, and electrochemical data. These findings would also provide important insights into the future design and synthesis of luminescent metal complexes and clusters with improved properties as well as novel molecular functional materials based on the utilization of these new metal complexes as building blocks. Such studies should contribute towards the future design and development of new molecular-based materials with desired properties through theoretical modeling and prediction as well as systematic fine-tuning of the properties, and may find applications in electroluminescence, luminescence chemosensing, and optoelectronic devices. It is envisaged that with the appropriate design of such metal-based materials and an in-depth study on the theoretical aspects of these classes of species, the proposed project should contribute not only to the basic understanding of the luminescence, redox, and electronic coupling behaviour of the newly prepared metal complexes and clusters and their structure-property relationship, but also to the advancement and future development of new advanced materials with desired improved properties.
Ab initio, EHMO, and DFT calculations have been performed on selected newly synthesized metal complexes and clusters. The results have been utilized to elucidate the structure, bonding, and spectroscopic and electrochemical properties of the metal complexes and clusters.
Contour plot of
(a) HOMO and (b) HOMO – 1 of
[Re(bpy)(CO)3(CºC-C6H4-CºC)Fe(C5H5)(dHpe)]
CACAO plot of
HOMO, LUMO, LUMO – 1, LUMO – 2 of ruthenium(II) polypyridine complexes with
orthometalled aminocarbene ligands
Molecular orbital
diagram for [Cu4(m-H2PCH2PH2)4(m4-S)]2+
Wang, C.-R.; Lo, K. K.-W.; Yam, V. W.-W. “Ab initio Study on Luminescence Chalcogenido Silver(I) Cluster [Ag4(m-H2PCH2PH2)4(m-E)]2+”, Chem. Phys. Lett., 1996, 262, 91-96.
Yam, V.W.-W.; Lo, K.K.-W.; Wang, C.-R.; Cheung, K.-K. “The First Series of Luminescent (m4-Chalcogenido)silver(I) Clusters”, Inorg. Chem., 1996, 35, 5116-5117.
Wang, C.-R.; Lo, K. K.-W.; Yam, V. W.-W. “Molecular Orbital Studies of Luminescent Silver(I) Chalcogenido Clusters”, J. Chem. Soc., Dalton Trans., 1997, 227-229.
Wang, C.-R.; Lo, K. K.-W.; Fung, W. K.-M.; Yam, V. W.-W. “Molecular Orbital Studies of Luminescent Tetranuclear Copper(I) Complexes”, Chem. Phys. Lett., 1998, 296, 505-514.
Yam, V.W.-W.; Lo, K.K.-W.; Fung, W.K.-M.; Wang, C.-R. “Design of Luminescent Polynuclear Copper(I) and Silver(I) Complexes with Chalcogenides and Acetylides as the Bridging Ligands”, Coord. Chem. Rev., 1998, 171, 17-41 (invited article).
Yam, V. W.-W.; Chong, S. H.-F.; Ko, C.-C.; Cheng, K.-K. “Synthesis and Luminescence Behaviour of Rhenium(I) Triynyl Complexes”, Organometallics, 2000, 19, 5092-5097.
Yam, V. W.-W.; Chu, B. W.-K.; Ko, C.-C.; Cheng, K.-K. “Synthesis, Structure, Luminescence and Electrochemical Studies of a Novel Class of Ruthenium(II) Polypyridine Complexes with Orthometallated Aminocarbene Ligands”, Dalton Trans., 2001, 1911-1919.
Lo, W.-Y.; Lam, C.-H.; Fung, W K.-M.; Sun H.-Z.; Yam, V. W.-W., Balcells, D.; Maseras, F.; Eisenstein, O. “An oscillating C22- unit inside copper rectangle ”, Chem. Commun., 2003, 1260-1261.
Wong, K. M.-C.; Lam, S. C.-F.; Ko C.-C.; Zhu N.-Y.; Yam V. W.-W.; Roue, S.; Lapinte, C.; Fathallah, S.; Costuas, K.; Kahlal, S.; Halet, J. F. “Electroswitchable photoluminescence activity: Synthesis, spectroscopy, electrochemistry, photophysics, and X-ray crystal and electronic structures of [Re(bpy)(CO)3(CºC-C6H4-CºC)Fe(C5Me5)-(dppe)](PF6)n (n=0, 1)”, Inorg. Chem., 2003, 42, 7086-7098.
The time for molecular calculation of one metal complex or cluster varies from several days to several weeks, depending on the number of atoms involved in the calculation. Most of our metal complexes and clusters are large in size and involve many atoms. Relativistic effects and spin-orbit coupling effects are also important in our systems. The calculations are usually very time-consuming. The installation of the high performance computer system would greatly reduce the computational time and would allow the parallel processing of several jobs in a simultaneous manner with less computational time.