The fluorescence and other photophysical parameters of highly polarized, quadrupolar bis-coumarins possessing an electron-rich pyrrolo[3,2- b ]pyrrole bridging unit are highly dependent on the linking position between both chromophores. Delocalization of the LUMO on the entire π-system results in intense emission and strong two-photon absorption.

An original approach has been developed for the insertion of formyl substituents at positions 2 and 5 of 1,4-dihydropyrrolo[3,2- b ]pyrroles by conversion of thiazol-2-yl substituents. The synthetic utility of these formyl groups was investigated, and a series of centrosymmetric A−π–D−π–A frameworks were constructed. The two-photon absorption of the quadrupolar pyrrolo[3,2- b ]pyrrole possessing two dicyanovinylidene flanking groups is attributed to an S 0 → (S 1 ) → S 4 transition which has a large TPA cross-section (1300 GM) for a molecule of this size.

To show that persistent high-spin polycarbenes can be realized by utilizing hetero spin systems, two diphenyldiazomethanes having pyridyl groups, i.e., bis{4-(4-pyridyl)-2,6-dimethylphenyl}diazomethane (4,4'-DPy-1-N(2)) and {2,4-di(4-pyridyl)-6-bromophenyl}(2,6-dimethyl-4-tert-butylphenyl)diazomethane (2,4-DPy-1-N(2)), were prepared. Triplet carbenes, 4,4'-DPy-1 and 2,4-DPy-1, generated by photolysis of the corresponding diazomethanes were characterized by spectroscopic means (ESR and UV/vis in matrix at low temperatures and laser flash photolysis in solution at room temperature). The results showed that they were fairly persistent. Magnetic properties of the photoproducts from a 1:1 complex between DPy-1-N(2) and Cu(hfac)(2) (hfac = hexafluoroacetylacetonate) were characterized by ESR and a superconducting quantum interference device (SQUID) magneto/susceptometer. The field dependences of magnetization for the complexes, expressed by using M versus H/T plots, were analyzed in terms of the Brillouin function to be S = 6.80 (F = 0.60) for the 1:1 complex of 4,4'-DPy-1 and Cu(hfac)(2) and S = 3.71 (F = 0.73) for the 1:1 complex of 2,4-DPy-1 and Cu(hfac)(2) at 2.0 K. Thus, it has been demonstrated that a high-spin species is actually generated in the photoproducts and that the complexed carbenes showed significant stability.