Efficient protocols for microwave‐assisted catalyzed amination of halogeno‐phenothiazines are described. Phenothiazine analogues of Tröger's base (PTB) were obtained by condensation of amino‐phenothiazines with formaldehyde in HCl/EtOH/H2O and structurally characterized by NMR and XRD analyses. The formation of PTB isomers was predicted by computational analysis based on theoretical methods (DFT and HF). Electronic properties of the parent amino‐phenothiazines and PTB were assessed on the basis of cyclic voltammetry and UV/Vis absorption/emission spectroscopy data. The compounds exhibit blue fluorescence emission characterized by extremely large Stokes shifts (8900–10300 cm–1) in both dilute solutions and aggregated states. Interactions with different types of biomolecules show the capacity of binding to proteins and DNA, with effects on prooxidant reactivity including lipid peroxidation.

Two bis-phospholane copper(I) metallamacrocycles were selectively synthesized starting from the same two building blocks, namely, ligand 1 and [Cu(NCCH)]BF. Reaction conditions (ligand:metal (L:M) ratio and dilution) can be tuned to obtain either a paddle-wheel- (2, L:M = 3:2) or box-type complex (3, L:M = 8:4). Their structures were unequivocally determined by X-ray crystallography. The solution P{H} NMR spectrum of complex 2 consists of a broad signal, as is common for such complexes, whereas complex 3 shows splitting of the P{H} NMR signal into a pseudoquartet due to Cu-P coupling, a rare occurrence exhibited only by highly symmetrical copper(I) phosphine complexes.

In a 2:2 reaction with silver(I) chloride or bromide, 1,5‐bis(1‐phospholano)pentane (1a) afforded frame‐like macrocyclic structures, with intra‐ (2, Cl) or intermolecular (3, Br) halido bridges. In contrast, 1,7‐bis(1‐phospholano)heptane (1b) formed coordination polymers 4a (Cl) and 4b (Br) with bridging bis‐phospholane and halido ligands. A unique paddle wheel‐type metallacryptand structure 5 was obtained from 1a and silver(I) bromide in a 2:3 reaction (M:L). All complexes were fully characterized by NMR, IR spectroscopy, mass spectrometry, and X‐ray crystallography.