A 2D honeycomb-shaped network based on a starburst cluster: [Ag4(micro3-Cl)(PPh2(CH2)2PPh2)1.5{S2P(OR)2}3](R = Et, Pri).

The first 2D metal-organic framework utilizing PPh2(CH2)2PPh2 (dppe) units as the linkers and tetranuclear silver clusters, [Ag4(micro3)-Cl){S2P(OR)2}3], as the network nodes in the formation of the honeycomb-shaped layer structure is reported.