The exchange interaction between two triplet carbene centers through diphenyl sulfide 4,4'-diyl, its sulfoxide and sulfone analogs, and thiaxanthene 2,7-diyl coupling units was studied. These dicarbenes were generated by photolysis of the corresponding bisdiazo precursors in MTHF matrices at cryogenic temperatures. From the temperature dependence of the ESR signals it was found that the dicarbene jointed through the sulfide group has a quintet ground state; it serves as a ferromagnetic coupler. On the other hand, as the oxidation state or the geometry of the sulfur atom was changed to sulfoxide, sulfone, and thiaxanthene groups, antiferromagnetic interaction was observed between the two diphenylcarbene units. The magnitude of the exchange interaction J/k was determined to be 11, -30, -92, and -21 K for diphenyl sulfide, sulfoxide, sulfone 4,4'-diyl, and thiaxanthene 2,7-diyl couplers, respectively. In the ESR spectra of sterically unconstrained sulfide and its analogs the isolated tripler signals were rather strong. In the thiaxanthene analog, however, this ratio of the isolated triplet signals to those of the other spin multiplicities was smaller. The isolated triplets were attributed to the conformation where the two phenyl rings were perpendicular to each other. It was demonstrated that the magnetic interaction could be tailored from ferro-to antiferromagnetic coupling by changing the oxidation state or geometry of the sulfur atom.