超分子化学的精彩之处在于其通过自组装实现了结构基元自发地从混乱到有序的变化,从而精准地构建复杂的结构。动态可逆的分子间相互作用是超分子可控自组装的基石,但其却导致传统超分子缺乏结构稳定性,从而限制了对超分子结构和性能的深入探索。如果能在超分子自组装精准构筑结构的基础上,通过简单的化学反应使之结构从动态可逆变为静态稳定,将有望一举解决以上难题,为超分子化学开辟崭新的方向。围绕上述设想,基于配位自组装,我们的研究方向围绕以下三个方面展开:
(1)发展类三联吡啶配体,利用新配体与金属配位作用在中性条件下动态可逆,而碱性条件下静态稳定的特性,构建兼具结构精准性和化学稳定性的配位超分子。
(2)基于新配体配位作用在酸碱调控下的动态-稳态变化,将其与传统配位作用及共价反应有机结合,进行自组装新方法的探索,设计并构筑出结构精妙、功能先进的配位超分子。
(3)我们将充分研究新配体给超分子带来的性质变化,包括电荷状态、金属价态、分子磁性、主客体作用等。结合超分子结构精准和化学稳定兼备的特性,我们致力于该类配位超分子材料在仿生催化、光电器件、量子计算与存储、生物医药等方面的应用探索。
Construction of assemblies from a pool of building block through “order-out-of-chaos” approaches is emerging as one of the ultimate goals of synthetic supramolecular chemistry in pursuing a higher level of precision and complexity. The dynamic nature of the intermolecular non-covalent interactions is the fundamental of well-controlled self-assembly, however, it brings traditional supramolecules insufficient stability for further structural design and functional investigations. We propose that the conversion of the non-covalent interaction feature from dynamic to static under mild conditions would solve the problem, and help to pave a new avenue in the field of supramolecular chemistry. With the goal of regulating interaction features, our research mainly focuses on the following aspects based on our research experiences in coordination-driven self-assembly.
(1) We aim to self-assemble 2D and 3D metallo-supramolecules with structural precision and high stability based on terpyridine analogues. These terpyridine analogues have reversible coordination with metal ions under neutral conditions, while the interaction turns to static and ultra-stable under basic conditions to concrete the structural frameworks.
(2) Based on the conversion of terpyridine analogues-metal ions complexation from dynamic to static, we aim to develop new self-assembly approaches through adding up traditional coordination-driven self-assembly and/or in-situ organic reactions. The new self-assembly approaches are expected to further advance the construction of complex structures and the exploration of functions.
(3) Beyond self-assembly, we are exploring these assemblies in diverse application fields, including catalysis, photoelectronic devices, quantum devices and biomedicine. These advanced functions will take full advantages of the dynamic-static transition brought about by the terpyridine analogues-metal ions complexation, as well as the charge states and redox states transitions, magnetic property regulations, and host-guest interactions.