We introduce relativistic density functional theory (DFT) calculations on the gold cluster complexes (cluster-molecule-cluster) Au-4-S-CnH2n-S'-Au'(4) (n = 2-5). The structural, electronic and relativistic (ZORA) Bader's quantum theory of atoms in molecules (QTAIM) properties of the two lowest-energy complex isomers were computed as a function of the alkanedithiol size (n). The lowest-energy isomer is a triplet spin state independently of the complex size. According to QTAIM, the Au-Au and S-Au bonds are classified as closed shell (non-covalent) type. The HOMO-LUMO gap of the cluster complexes shows a zigzag behavior typical of gold nanoclusters with respect to the size of the alkanedithiol chain (n). (C) 2016 Elsevier B.V. All rights reserved.