Diazodi(4-pyridyl)methane and Mn(hfac)(2) formed the orange-colored 1:1 complex having a spiral 1-D chain structure. While all the Mn (II) ions were found to be magnetically isolated before irradiation, a 1-D ferrimagnetic chain was established in the complex by an antiferromagnetic interaction of the 3d spins of Mn(II) with the 2p spins of photochemically generated carbenes (S = 2/2). Dark greenish bricks of the similar 1 : 1 complex from the diazo compound and Cu(hfac)(2) exhibited after photolysis a T-chi mol - T profile characteristic of ferromagnetic interaction between the carbenes and the Cu(II) ions. The carbene centers were found to be stable up to ca. 230 K in both the complexes. The photochemically generated heterospin system will serve as a prototype of molecular photomagnetic recording devices.