Four　new　inorganic　supramolecular　complexes,　[Hg4P　2][ZrCl6]　(1),　[Hg4As2][ZrCl　6]　(2),　[Hg4P2][HfCl6]　(3),　and　[Hg4As2][HfCl6]　(4),　have　been　prepared　by　moderate-temperature　solid-state　reactions.　All　compounds　crystallize　in　the　space　group　Pbca　of　the　orthorhombic　system　with　Z　=　8.　Their　structures　are　built　up　of　mercury　pnictide　cationic　hosts　and　distorted　octahedral　[MCl　6]2-　(M　=　Zr,　Hf)　guests.　The　isolated　octahedral　guests　consist　of　tetravalent　Zr4+　and　Hf4+　cations　coordinated　by　chlorine　atoms　and　are　embedded　in　the　infinite　channels　formed　by　the　host　framework.　Their　optical　properties　were　investigated　in　terms　of　their　diffuse　reflectance　and　FTIR　spectra.　The　electronic　band　structures　along　with　densities　of　states　(DOS)　calculated　by　DFT　indicate　that　all　of　the　title　compounds　are　semiconductors　with　direct　band　gaps,　and　their　optical　absorptions　mainly　originate　from　charge　transitions　from　Cl　3p　and　P　3p/As　4p　states　to　Hg　6s,　Hg　5p,　and　Zr　4d/Hf　5d　states.　Optical　dielectric　constant　calculations　show　that　1-4　possess　dielectric　anisotropy,　which　is　consistent　with　their　structural　studies.　Four　quaternary　inorganic　supramolecular　[Hg　4Z2][MCl6]　(Z　=　P,　As;　M　=　Zr,　Hf)　complexes　have　been　prepared　by　solid-state　reactions.　They　are　the　first　mercury　pnictide　halides　containing　d　transition-metal　cations,　and　their　syntheses,　crystal　and　band　structures,　and　optical　properties　are　reported.　Copyright　©　2013　WILEY-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim.