Theoretical investigation of the topology and metalation effects on the first hyperpolarizability of rosarins

The static first hyperpolarizabilities (beta(0)) of several free-based and metal-doped rosarins were extracted from density functional theory (DFT) calculations. The calculated beta(0) value of the upward opening calix[n]pyrrole is almost 4.5 times larger than that of the downward one profiting from the greater separation of charge. Doping an alkali atom into the free-based rosarin can obtain a cation-anion separation molecule with enormous hyperpolarizability. The electride Cs@calix[6]pyrroles have considerably large beta(0) values with 31 002 and 82 647 a.u. for upward and downward opening configurations, while the beta(0) values of the related calix[6]pyrroles are only 784 and 3532 a.u., respectively. (C) 2015 Elsevier B.V. All rights reserved.