How far can we push chemical self-assembly? This is one of the
current big questions in science. Hydrogen bonds and the coordination
of metal ions have been the most-commonly used forces to drive
the spontaneous organization of small building blocks into large,
complex, and sometimes functional structures. The use of pi-stacking
and van der Waals forces is now well documented. Other intermolecular
forces have not been used mostly because they have been poorly
understood until now, as is the case for the inter-atomic contacts
made by the heavy p-block elements. The succession of names given
to this phenomenon parallels the evolution of our understanding:
the initial 'non-bonded contact" became"weakly bonding
interaction" and now the term "secondary bonding interaction"(SBI)
is gaining increasing acceptance.
Our research program pursues the use of SBIs of heavy p-block
elements in supramolecular chemistry and molecular self-assembly.
SBIs have distinctive features that can be exploited to control
the properties of self-assembled materials. For example, while
hydrogen bonds are barriers to electron mobility, SBIs enhance
conductivity. In addition, SBIs can stabilize compounds with unusual
compositions. In summary, new interactions translate in new properties.
Noncentrosymmetric supramolecular structures exhibit nonlinear
optical (NLO) properties, there are many known examples of supramolecular
NLO materials built with hydrogen bonds. However, hydrogen bonds
absorb light in the near-infrared and such materials are not useful
in optical fibre technology. SBIs vibrate at much lower frequencies
and their supramolecular nonlinear optical materials should have
greater transparency. An additional advantage to using heavy elements,
the soft electron clouds of these atoms result in unusually strong
nonlinear properties. This is precisely a second major interest
of our group. We have designed and synthesized molecules with
promising nonlinear activity and have developed our own Second
Harmonic Generation spectrometer with a tunable excitation wavelength.