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A new series of cationic heterodinuclear complexes, [M1M2Cl2(meso‐dpmppp)(RNC)2]PF6 (M1=Ni, M2=Rh, R=tBu (1 a); M1=Pd, M2=Rh, R=tBu (2 a), Xyl (2 b); M1=Pt, M2=Rh, R=tBu (3 a), Xyl (3 b); M1=Pd, M2=Ir, R=tBu (4 a)), supported by a tetradentate phosphine ligand, meso‐Ph2PCH2P(Ph)(CH2)3P(Ph)CH2PPh2 (meso‐dpmppp), were synthesized by stepwise reactions of meso‐dpmppp with NiCl2 ⋅ 6H2O or MCl2(cod) (M=Pd, Pt), forming mononuclear metalloligands of [M1Cl2(meso‐dpmppp)], and with [M2Cl(cod)]2 (M2=Rh, Ir) and RNC (R=tBu, Xyl) in the presence of [NH4][PF6]. The related neutral PdRh complex, [PdRhCl3(meso‐dpmppp)(XylNC)] (5), was also prepared. The structures of 1–5 were determined by X‐ray analyses to contain two square planar d8 metal centers with face‐to‐face arrangement, where meso‐dpmppp supports M1 and M2 metal ions in cis/trans‐P,P coordination mode, combining cis‐{M1P2Cl2} and trans‐{M2P2(CNR)2} units. Complexes 1–4 showed an intence characteristic absorption around 422–464 nm derived from RhI→RNC MLCT transition (HOMO→LUMO+1), which are influenced by changing M1 (NiII, PdII, PtII) metal ions since HOMO composed of dσ* orbitals appreciably destabilized by changing M1 from Ni to Pd, and Pt. The electronic structures of 1 a–4 a were investigated on the basis of DFT calculations and NBO analyses to show weak but noticeable d8–d8 metallophilic interaction as empirical dispersion energy of 0.9–1.5 kcal/mol without M1–M2 covalent bonding interaction. In addition, 1–5 were utilized as catalysts for hydrosilylation of styrene, and the NiRh complex 1 a was found to show higher activity and chemo‐ and regioselectivity compared with 2–5. [ABSTRACT FROM AUTHOR]

The dynamical functions of molecular metal chains, that could be derived from unique physical and chemical properties coupled with self-assembly of metal chain components, have largely been unexplored, and this review paper focuses on the dynamic behaviours of Pd chains supported by linear tetraphosphines, meso- and rac-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 recently reported, and the current development on fine-tuning of metal chains by introducing heterometal atoms, i.e. heterometallic molecular metal chains, that are considered as promising dynamical components in the next generation. [ABSTRACT FROM AUTHOR]

With the hope of tuning structural and electronic properties of the metal chains by changing the N‐substituent group and P‐chiral configurations, a series of PNP bridged tetraphosphines, rac‐ and meso‐Ph2PCH2P(Ph)N(Ar)P(Ph)CH2PPh2 (Ar=4‐RC6H4, R=F (rac‐dpmppanF), CH3 (rac‐dpmppanMe), H (meso‐dpmppan), OMe (meso‐dpmppanOMe); Ar=2,4‐xylyl (rac‐dpmppanMe2)), were synthesized, and utilized to prepare the Pd4 and Pt2Pd2 chains with XylNC terminal ligands, [M4(rac‐dpmppanR)2(XylNC)2](PF6)2 (M4=Pd4, R=F (1F), Me (1Me); M4=Pt2Pd2, R=F (4F), Me (4Me)) and [M4(meso‐dpmppanR)2(XylNC)2](PF6)2 (M4=Pd4, R=H (6), OMe (6OMe); M4=PdPt2Pd, R=OMe (9OMe)). While the M4 metal chains with rac‐dpmppanR (R=H, F, Me) ligands showed only marginal effects on the tetranuclear metal chains, the meso stereoisomer of meso‐dpmppanOMe afforded a new series of Pd4 (6OMe), PtPd3 (7OMe), PtPd2Pt (8OMe), PdPt2Pd (9OMe), Pt3Pd (10OMe), and Pt4 (11OMe) chains that exhibited a characteristic electronic absorption band tunable by the number and positions of incorporated Pt atoms from 628 nm to 473 nm. Especially, 11OMe is the first example of Pt4 chains supported by tetraphosphines. The coordinatively unsaturated Pd4 strings, [Pd4(rac‐dpmppan)2(CH3CN)](BF4)2 (12) and [Pd4(meso‐dpmppanOMe)2](BF4)2 (13), were also synthesized and 12 was utilized in axial ligand exchange reactions with PPh2Me, and PPh3 to disclose their successive incorporation into [Pd4(rac‐dpmppan)2(L)2](BF4)2 (L=PPh2Me (14 a), PPh3 (14 b)) and remarkable red‐shift (713–718 nm) of the HOMO‐LUMO transition of the Pd4 chains. The linear Pd4, PtnPd4‐n (n=1–3), and Pt4 complexes obtained in the present study could be useful 1D building blocks for assembling through metal−metal interaction. [ABSTRACT FROM AUTHOR]

The synthesis and characterization of tri- and tetranuclear Cu(II) complexes utilizing mononuclear Cu(II) chiral building block with the sugar-derived Schiff's base ligand H3L(super 1) are reported. The results help in creating an efficient method for constructing chiral multinuclear complexes by utilizing the mononuclear {Cu(HL(super 1))} chiral building blocks.

Research has been conducted on the 1,3-propanadiamine derivatives connected to carbohydrates and prepared from peracetylated sugar and 1,3-dibromo-2-propanol. Anomeric configurations and sugar puckering conformations have been investigated via X-ray crystallography of diazido precursors.

Research has been conducted on the heptadentate N-glycoside ligand mononuclear manganese(II) complexes. The use of X-ray crystallography has been described.

A P‐stereogenic linear tetraphosphine tetraoxide, (R,R)‐ or (S,S)‐dpmppm(=O)4, was synthesized to prepare C2 dinuclear M(hfa)3 complexes (M=Eu, Tb, Y) as the first example of lanthanide(III) complexes with P‐chiral multidentate phosphine oxides. The mononuclear M(hfa)3 complexes (M=Eu, Y) with a P‐chiral diphosphine dioxide, tpdpb(=O)2, were also prepared, and comparison of their photophysical properties for the EuIII complexes revealed that significant chiral induction from the P‐chiral centers arises on the achiral M(hfa)3 units through intramolecular π‐π stacking constraint in the dinuclear system. [ABSTRACT FROM AUTHOR]

Carbohydrates are widely occurring and are needed by living organisms. Naturally rare carbohydrates are involved in glycoproteins, glycolipids and antibiotics. The syntheses and structural determinations of novel seven-coordinated cage-type cobalt(II) compounds, containing N-glycosides from mannose-type aldoses is reported.

Incorporation of a monovalent group 11 metal ion (Au(I), Ag(I) or CU(I)) with d10 configuration into the Pt2 core has led to the formation of heterotrimetallic Pt2M complexes. The PtCuX assembly forms a rhombic structure when CuX fragment was introduced. The reactions could help in the synthesis of other heterotrinuclear complexes. The angle of Pt...Cu-X is less than 90 degrees resulting in a short interatomic distance between the terminal Pt and X atoms.

The synthesis and characterization of carboxylate-bridged dimagnesium(II) complexes containing the dinucleating XDK ligand where H2XDK = m-xylylenediamine bis(Kemp's triacid imide) were carried out. Consequently,, carboxylate- and phosphodiester-bridged dimagnesium(II)-XDK, dicalcium(II)-XDK and dizinc(II)-XDK complexes were prepared and found to be catalysts in the cleavage of phosphate ester bonds.

The reaction of (RuCl2(dmso)4) with dhptaH5 (1,3-diamino-2-hydroxypropane tetraacetic acid) and carboxylate ligands afforded diruthenium(III) complexes, M(Ru(dhpta)(mu-O2Cr)2). The complexes arer soluble and retain the dinuclear structure in water. They thus offer a good basis for clarifying redox properties of the diruthenium center. X-ray crystallography and EXAFS analysis were used to characterize the complexes.

Aldoses are coordinated on nickel(II) ion using the N-glycosidic bond formation with tris(2-aminoethyl)amine (tren). Specifically, mono-, bis- and tris-(sugar)complexes are synthesized and characterized. For example, (Ni tren H2O2)X2, where X = Cl, Br and X2 = SO4, reacts with mannose-type aldoses of 2,3-cis configuration (D-mannose and L-rhamnose) to yield bis(N-aldosyl-2-aminoethyl)(2-aminoethyl)amine nickel(II) complexes (Ni N,N'-aldosyl sub 2-tren)X2. The resulting complexes are characterized by X-ray analyses.

The reactions of linear trinuclear platinum complexes with small organic molecules yields asymmetrical A-frame triplatinum complexes. The complexes possess an extra bridge across one of the metal-metal bonds. The trinuclear complexes serve as models for the study of the interactions between small molecules and the surfaces of heterogeneous catalysts. The reactions of a linear triplatinum complex with electron deficient HBF4.Et2O and p-NO2C6H4NC are discussed.

The addition of Zn(acac)2.2H2O to [Zn(XDK)(H2O)] XDK mononuclear zinc complex will produce the dizinc compound [Zn2(XDK)(acac)2(CH3OH)2]. [Zn2(XDK)(acac)2(CH3OH)2] has four discrete molecules in its unit cells intermolecular contacts. [Zn(XDK)(H2O)] acts as a precursor to zinc-containing carboxylate-bridged heterodimetallic complexes. The Zn to M distance is linearly coordinated with the ionic radius of high-spin octahedral M ions. Carboxylate-bridged divalent heterodinuclear compounds acts models for heterodimetallic centers in nonredox metalloenzymes.

The linear Pd8 complex supported by tetraphosphines reacted with HBF4 to give an unprecedented linear tetrapalladium complex with a terminal hydride, which promoted electrocatalytic hydrogen formation from HBF4 in acetonitrile. The 1D coordination polymer of Pd8 chain confined within Nafion film was applied to the electrocatalytic H2 formation. [ABSTRACT FROM AUTHOR]

Reactions of Pd8 strings supported by meso‐Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso‐dpmppm) ligands, [Pd8(meso‐dpmppm)4(L)2]4+ (L=CH3CN (1), XylNC (2)) with C60 resulted in the exclusive formation of unprecedented metal‐chain‐wired C60 bucky balls, [{Pd4(meso‐dpmppm)2(L)}2(C60)]4+ (L=CH3CN (11), XylNC (12)), in which a C60 fullerene is trapped in the central Pd–Pd junction, as unambiguously established by spectroscopic, X‐ray crystallographic, and theoretical techniques. The similar reaction of Pd8 strings supported by rac‐dpmppm, [Pd8(rac‐dpmppm)4(CH3CN)2]4+ (3) also afforded a racemic mixture of [{Pd4((R*,R*)‐dpmppm)2(CH3CN)}2(C60)]4+ (13) without scrambling the Pd4 fragments with (R,R)‐ and (S,S)‐dpmppm ligands. Consequently, those of enantiopure chiral Pd8 strings, [Pd8((R*,R*)‐dpmppm)4(CH3CN)2]4+, certainly afforded chiral bucky balls of [{Pd4((R*,R*)‐dpmppm)2(CH3CN)}2(C60)]4+ (13RR and 13SS), that exhibit mirror‐image circular dichroism spectra. The reactions of 1 and 2 were also applied for trapping a C70 fullerene to give 2 : 1 adducts of [{Pd4(meso‐dpmppm)2(L)}2(C70)]4+ (L=CH3CN (21), XylNC (22)). These results provide useful information for creating a platform to develop dimensionally and chirality controlled metal–carbon nanocomposite materials. [ABSTRACT FROM AUTHOR]

Dinuclear manganese(II) complex, Mn2(XDK)(NO3)(CH3OH)4(H2O2)NO3 can be synthesized by reacting Mn(NO3)2*6H2O with Na2XDK.4H2O. X-ray crystallographic analysis reveals that the cation in the resulting compound contains two octahedral Mn(II) ions attached by two molecules and a nitrate ion. Compound 1 exist in three oxidation states and is suitable for the synthesis of various bis(mu-carboxylato)dimanganese (II) complexes with N-donor bidentate terminal ligand. Synthesis of bis(mu-carboxylato)dimanganese (II) complexes is discussed.

The reaction between Zn(NO3)2.6H2O, H2XDK and NaOH yields the mononuclear zinc complex (Zn{XDK}{H2O}), which on further reaction with Zn(acac)2.2H20 leads to the asymmetrical dinuclear complex (Zn2{XDK}{acac}2{CH3OH}2).H2O. A dizinc structure bridged by XDK and acac ligands is detected, where the zinc atoms have a trigonal bipyramidal and octahedral geometry. The dizinc complex (Zn2{XDK}{NO3}2{CH3OH}{H2O}2) obtained from 1 reacts with phosphate ester salts to give the phosphate-bridged dinuclear zinc complexes.

An incomplete cubane-type cluster reacted with Pd black in aqueous HCl to yield a mixed-metal cubane-type cluster having a novel PdMO3S4 core. The structural properties and synthesis of these compounds were studied as models of active sites in biological catalysts. Mixed-metal sulfur clusters containing noble metals promoted stoichiometric and catalytic reactions.

The reaction of benzoic PdCl2(RNC)2 solution, where R is 2,6-Me2C6H3, with K(C5Ph5) followed by residual extraction alumina chromatography elution and hexane addition yields the binuclear Pd(I) isocyanide complex, Pd2(eta-5-C5Ph5)2(mu-2, 6-Me2C6H3NC)2.1.5 C6H6 in violet crystalline form. The Pd(I) complex and other such Pd(I) isocyanide complexes have weak Pd-Pd bond interactions due to full sigma and pi orbital occupancy in the dimer. The Pd-Pd bond distances are in the range 2.632 to 2.757 angstroms.

Diphosphine (diphos), aromatic isocyanide (RNC) and NH4PF6 reacted with PdCl2 (COD) to produce RNC and diphos ligands in monocellular palladium(II) complexes. A binuclear palladium(I) complex was derived from a controlled-potential electrolysis of the diphos ligand complexes at a platinum-plate electrode-consumed 1 F per mol in acetonitrile -1.6 V. Electronic, IR and H and P(H) NMR spectroscopies, X-ray crystallography and extended X-ray absorption five structure (EXAFS) were used to determine the properties of the binuclear palladium(I) complex.

The spontaneous adsorption and fixation of CO2 in air through the Ni(II) ethanol gives the trinuclear nickel(II) complex /Ni3(N,N-Me2en)6(CO3)(H2O)4~(ClO4)4. The trinuclear complex has a structure a = 25.824(7) Angstrom (A), c = 14.506(3) A, Z = 6 and space group P6(sub 3). It consists of three octahedral nickel(II) complexes connected by hydrogen bonds around the carbonate ligand. This bonding system may result in the spontaneous fixation of CO2 in air.

A series of the octapalladium chains supported by meso‐Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso‐dpmppm) ligands, [Pd8(meso‐dpmppm)4(L)2](BF4)4 (L=none (1), solvents: CH3CN (2 a), dmf (2 b), dmso (2 c), RN≡C: R=Xyl (3 a), Mes (3 b), Dip (3 c), tBu (3 d), Cy (3 e), CH3(CH2)7 (3 f), CH3(CH2)11 (3 g), CH3(CH2)17 (3 h)) and [Pd8(meso‐dpmppm)4(X)2](BF4)2 (X=Cl (4 a), N3 (4 b), CN (4 c), SCN (4 d)), were synthesized by using 2 a as a stable good precursor, and characterized by spectroscopic (IR, 1H and 31P NMR, UV‐vis‐NIR, ESI‐MS) measurements and X‐ray crystallographic analyses (for 1, 2 a, b, 3 a, b, e, f, 4 a–d). On the basis of DFT calculations on the X‐ray determined structure of 2 b ([2b‐Pd8]4+) and the optimized models [Pd8(meso‐Ph2PCH2P(H)CH2P(H)CH2PH2)4(CH3CN)2]4+ ([Pd8Ph8]4+) and [Pd8(meso‐H2PCH2P(H)CH2P(H)CH2PH2)4(CH3CN)2]4+ ([Pd8H8]4+), with and without empirically calculating dispersion force stabilization energy (B3LYP‐D3, B3LYP), the formation energy between the two Pd4 fragments is assumed to involve mainly noncovalent interactions (ca. −70 kcal/mol) with four sets of interligand C−H/π interactions and Pd⋅⋅⋅Pd metallophilic one, while electron shared covalent interactions are almost canceled out within the Pd8 chain. All the compounds isolated are stable in solution and exhibit characteristic absorption at ∼900 nm, which is assignable to a spin allowed HOMO to LUMO transition, and shows temperature dependent intensity change with variable absorption coefficients presumably due to coupling with some thermal vibrations. The structures and electronic states of the Pd8 chains are found finely tunable by varying the terminal capping ligands. In particular, theoretical calculations elucidated that the HOMO‐LUMO energy gap is systematically related to the central Pd−Pd distance (2.7319(6)–2.7575(6) Å) by two ways with neutral ligands L (1, 2, 3) and with anionic ligands X (4), which are reflected on the NIR absorption energy of 867–954 nm. The isocyanide terminated Pd8 complexes (3) further reacted with excess of RNC (6 eq) to afford the Pd4 complexes, [Pd4(meso‐dpmppm)2(RNC)2](BF4)2 (13), and the cyclic voltammograms of 2 a (L=CH3CN), 3, and 13 (R=Xyl, Mes, tBu, Cy) demonstrated wide range redox behaviors from 2{Pd4}4+ to 2{Pd4}0 through 2{Pd4}2+↔{Pd8}4+, {Pd8}3+, and {Pd8}2+ strings. The oxidized complexes, [Pd4(meso‐dpmppm)2(RNC)3](BF4)4 (16), were characterized by X‐ray analyses, and the two‐electron reduced chain of [Pd8(meso‐dpmppm)4](BF4)2 (7) was analyzed by spectroscopic and electrochemical techniques and DFT calculations. Reactions of 2 a with 1 equiv. of aromatic linear bisisocyanide (BI) in CH2Cl2 deposited insoluble coordination polymers, {[Pd8(meso‐dpmppm)4(BI)](BF4)4}n (5), and interestingly, they were soluble in acetonitrile, 31P{1H} and 1H DOSY NMR spectra as well as SAXS curves suggesting that the coordination polymers may exist in acetonitrile as dynamically 1D self‐assembled coordination polymers comprising ca. 50 units of the Pd8 rod averaged within the timescale. [ABSTRACT FROM AUTHOR]

The novel tetranuclear copper(II) complexes with alpha-D-glucose-1-phosphates, [Cu(sub 4)(mu-OH)(alpha-D-Glc-1P)(sub 2)(L)(sub 4)(H2O)2(sub 2)](NO3)(sub 3) were prepared and characterized by X-ray crystallography. Complex [Cu(sub 4)(mu-OH)(alpha-D-Glc-1P)(sub 2)(L)(sub 4)(H2O)2(sub 2)](NO3)(sub 3) was revealed to be a good precursor of the adenosine 5'-triphosphate (ATP) stabilized tetranuclear Cu(super II) complex of [Cu4(ATP)2(bpy)4].

Copper hydride compounds have attracted interest in diverse fields as base metallic material in place of rare and noble metals, which have widely been utilized in hydrogenation catalysts, hydrogen storage, and electrochemical materials. Since the first report on the synthesis of copper hydride complex [Cu6H6(PPh3)6] in 1971, copper hydride reagents have been utilized in a variety of organic transformation. While well‐characterized copper hydride complexes have been long limited to a few examples, recently several research groups have reported the synthesis of phosphine‐stabilized copper hydride complexes with various metal‐frameworks and unique reactivity. Here we review recent progress on the synthesis and structures of copper hydride complexes supported by phosphine ligands, including di‐, tri‐, and tetraphosphines, and also describe their reactivity with CO2. [ABSTRACT FROM AUTHOR]

The synthesis and characterization for a D-Glc-1P-bridged tetranuclear copper(II) complexes, [[Cu4(mu-OH){mu-(alpha-D-Gle-1P)}2(L)4(H2O)2].sup.3+] and its Cu4 core transformation through incorporation of a series of sugar acids is presented. These complexes are revealed to incorporate a series of sugar acids through the Cu4 core structural changes, affording the sugar-coated rectangular Cu4 clusters and linearly ordered chiral coordination polymers.

A synthesis of biscarboxylate-bridged dicopper(II) complexes containing a series of sugar phosphate esters by utilizing the biscarboxylate ligand XDK (H(sub 2)XDK=m-xylenediamine bis(Kemp's triacid imide)) and imine-based chelating ligands is studied. The XDK has proved to be an efficient dinucleating ligand in stabilizing a variety of dinuclear metal centers.

Reaction of [Cu(MeCN)4]BF4 with rac‐Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (rac‐dpmppm) gave [Cu2(µ‐rac‐dpmppm)(MeCN)4](BF4)2 (1), and that of CuCl with rac‐dpmppm in the presence of 2,6‐xylyl isocyanide (XylNC) and NH4PF6 afforded [Cu2(µ‐rac‐dpmppm)(XylNC)4](PF6)2 (2). Complex 1 was converted by treatment with diimino ligands (N^N) to a series of CuI2 complexes, [Cu2(µ‐rac‐dpmppm)(N^N)2]2+ (N^N = phen (3), 4‐Mephen (4), 4,7‐Me2phen (5), 5,6‐Me2phen (6), 2,9‐Me2phen (7), 3,4,7,8‐Me4phen (8), 4,7‐Ph2phen (9), bpy (10), 4,4′‐Me2bpy (11), and 1,8‐naphtyridine (nap) (12)), where phen = 1,10‐phenanthroline and bpy = 2,2′‐bipyridyl. The isolated complexes were characterized by spectroscopic and X‐ray crystallographic analyses to reveal that two CuI ions are triply bridged by a rac‐dpmppm ligand in κ2,κ2 fashion resulting in robust Z‐form dicopper structures, where the Cu···Cu distances vary from 4.2 to 5.6 Å depending on the ancillary ligands through altering conformation of the fused six‐membered chelate rings. The bulky ligands of XylNC and 2,9‐Me2phen deform the conformation to boat (2) and twist boat (7) forms, leading to elongation of Cu···Cu separation (Cu···Cu = 5.3488(5) Å (2), 5.5681(6) Å (7)), and other non‐bulky ligands render them deformed chair forms with Cu···Cu = 4.2051(5) Å (8) to 4.7341(5) Å (10). The solution behaviors of 5 and 11 were examined by variable temperature 1H NMR measurements to show fluxional exchange of the two nitrogen atoms attaching to the tetrahedral Cu centers with ΔG‡ of 14 kcal/mol at room temperature. Photophysical properties of 3–12 were also investigated to show rapid fluorescence at 394–467 nm in CH2Cl2 solutions and phosphorescence at 582–608 nm in the solid states. Reaction of [Cu(MeCN)4]BF4 with rac‐dpmppm and NaBH4 in MeOH/CHCl3 afforded [Cu4(µ4‐H)(µ‐Cl)2(µ‐rac‐dpmppm)2]BF4 (13), in which two rac‐dpmppm ligands exhibited a new coordination mode of κ2,κ1,κ1 M3‐bridge to hold two {Cu2(µ‐Cl)(µ‐rac‐dpmppm)}+ units connected by a central µ4‐hydride. [ABSTRACT FROM AUTHOR]

Reaction of [Cu(MeCN)4]BF4 with rac‐Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (rac‐dpmppm) gave [Cu2(µ‐rac‐dpmppm)(MeCN)4](BF4)2 (1), and that of CuCl with rac‐dpmppm in the presence of 2,6‐xylyl isocyanide (XylNC) and NH4PF6 afforded [Cu2(µ‐rac‐dpmppm)(XylNC)4](PF6)2 (2). Complex 1 was converted by treatment with diimino ligands (N^N) to a series of CuI2 complexes, [Cu2(µ‐rac‐dpmppm)(N^N)2]2+ (N^N = phen (3), 4‐Mephen (4), 4,7‐Me2phen (5), 5,6‐Me2phen (6), 2,9‐Me2phen (7), 3,4,7,8‐Me4phen (8), 4,7‐Ph2phen (9), bpy (10), 4,4′‐Me2bpy (11), and 1,8‐naphtyridine (nap) (12)), where phen = 1,10‐phenanthroline and bpy = 2,2′‐bipyridyl. The isolated complexes were characterized by spectroscopic and X‐ray crystallographic analyses to reveal that two CuI ions are triply bridged by a rac‐dpmppm ligand in κ2,κ2 fashion resulting in robust Z‐form dicopper structures, where the Cu···Cu distances vary from 4.2 to 5.6 Å depending on the ancillary ligands through altering conformation of the fused six‐membered chelate rings. The bulky ligands of XylNC and 2,9‐Me2phen deform the conformation to boat (2) and twist boat (7) forms, leading to elongation of Cu···Cu separation (Cu···Cu = 5.3488(5) Å (2), 5.5681(6) Å (7)), and other non‐bulky ligands render them deformed chair forms with Cu···Cu = 4.2051(5) Å (8) to 4.7341(5) Å (10). The solution behaviors of 5 and 11 were examined by variable temperature 1H NMR measurements to show fluxional exchange of the two nitrogen atoms attaching to the tetrahedral Cu centers with ΔG‡ of 14 kcal/mol at room temperature. Photophysical properties of 3–12 were also investigated to show rapid fluorescence at 394–467 nm in CH2Cl2 solutions and phosphorescence at 582–608 nm in the solid states. Reaction of [Cu(MeCN)4]BF4 with rac‐dpmppm and NaBH4 in MeOH/CHCl3 afforded [Cu4(µ4‐H)(µ‐Cl)2(µ‐rac‐dpmppm)2]BF4 (13), in which two rac‐dpmppm ligands exhibited a new coordination mode of κ2,κ1,κ1 M3‐bridge to hold two {Cu2(µ‐Cl)(µ‐rac‐dpmppm)}+ units connected by a central µ4‐hydride. [ABSTRACT FROM AUTHOR]