Abstract: | The cluster compounds, [MoAu2S4(PPh2Py)2] ( 1 ) and [WAu2S4(PPh2Py)2] ( 2 ), were synthesized by the reaction of (NH4)2MS4 (M = Mo, W), H[AuCl4]·4H2O and diphenyl‐2‐pyridyl‐phosphine (PPh2Py) in CH2Cl2 solution. [MoAu2S4(PPh2Py)2] crystallizes in the monoclinic space group P21/c with a = 18.385(2), b =12.304(1), c = 16.904(2) Å, β =110.722(2)°, and Z = 4. [WAu2S4(PPh2Py)2] crystallizes in the triclinic space group P‐1 with a = 9.333 (3), b = 10.628(3), c = 19.566(6) Å, α = 89.26(1), β = 80.87(1), γ = 68.85(1)°, and Z = 2. Single crystal X‐ray analysis showed that these two compounds are isostructural, but belong to different space groups. The Mo (W) atom has a slightly distorted tetrahedral coordination, and the two Au atoms are distorted from trigonal planar, the P—Au—M—Au—P chain is nearly linear. Measurement of the nonlinear optical (NLO) properties using the Z‐scan technique with an 8‐ns pulsed laser at 532 nm showed that 1 and 2 possess NLO absorption and effective self‐focusing effect. The effective α2 and n2 values of cluster 1 are 5.89 × 10—12 m · W—1 and 6.45 × 10—18 m2 · W—1; the effective α2 and n2 values of compound 2 are 4.35 × 10—11 m · W—1 and 3.73 × 10—17 m2 · W—1. |