The design and two-component [2 + 3] self-assembly of a series of new organometallic molecular prisms (3a-d) are described. Assemblies 3a,b incorporate 4,4',4'-tris[ethynyl-trans-Pt(PEt2)2(N0 3)]triphenylamine (la) containing a Pt-ethynyl functionality as tritopic planar acceptor and organic "clips" 2a and 2b, respectively [where 2a = l,3-bis(3-pyridyl)isophthalic amide; 2b = l,3-bis(ethynyl3-pyridyl) benzene]. In a complementary approach an organic tritopic planar donor ligand 2c [2c = 4,4',4'-tris(4-pyridylethynyl)triphenylamine] was assembled with an organometallic "clip", 1,8-bis[{trans-Pt(PEt3) 2(N03)}ethynyl]anthracene (lb), to obtain prism 3c. A new organometallic carboncentered acceptor, l,l,l-tris[4-{trans-Pt(PEt 3)2(N03)}ethynylphenyl]ethane (1c), has been prepared and its prism derivative (3d) using an organic "clip" is prepared. Assemblies (3a-d) were characterized by multinuclear NMR spectroscopy, electrospray ionization mass spectroscopy and elemental analysis. 3a-d showed fluorescence behavior in solution and quenching of fluorescence intensity (3a, 3c-d) was noticed upon addition of TNT (2,4,6-trinitrotoluene), a common constituent of many commercial explosives. A thin film of the assembly 3d made by spin coating of a solution of 3x 10-5 M in DMF on a 1 cm 2 quartz plate showed fluorescence response to the vapor of TNT. Copy; 2009 American Chemical Society.