Derivatives of 1,2-dithienylethene (DTE)h ave superb photochromic properties due to an efficient reversible photocyclization reaction of their hexatriene structure and, thus, have application potential in materials for optoelectronics and (multi-responsive) molecular switches. Transition-metal complexes bearing switchable DTE motifsc ommonly incorporate their coordination site ratherd istantf rom the hexatriene system.I nt his work the redoxa ctive ligand 1,2-bis(2,5-dimethylthiophen-3-yl)ethane-1,2-dione is described,w hich reacts with [V(TMEDA) 2 Cl 2 ]t og ive ar are nonoxido vanadium(IV) species 3(M,M/P,P).T his blue complex has two bidentate en-diolato ligandsw hich chelate the V IV center and give rise to two five-membered metallacycles with the adjacent hexatriene DTE backboneb earing axial chirality.U pon irradiation with UVAl ight or prolonged heating in solution, the blue compound 3(M,M/P,P) converts into the purple atropisomer 4(para,M/para,P).B othc omplexes were isolated and structurally characterized by single-crystal X-ray diffraction analysis (using lab source and synchrotron radiation). The antiparallel configuration( M or P helicity) present in both 3(M,M/P,P) and 4(para,M/para,P) is aprerequisite for (reversible)6 p cyclization reactions. AC WE PR spectroscopic study reveals the metalloradical character for 3(M,M/P,P) and 4(para,M/para,P) and indicatesd ynamic reversible cyclization of the DTE backbonei nc omplex 3(M,M/ P, P ) at ambient temperature in solution.