Nanopore-induced host-guest charge transfer phenomena in a metal-organic framework.

A spontaneous entrapment of electron-donating small guest molecules, including tetrathiafulvalene (TTF) and N,N,N',N'-tetramethyl-1,3-propanediamine (TMPDA), was realized in a structurally flexible metal-organic framework, {Mn7(2,7-AQDC)6(2,6-AQDC)(DMA)6}∞ (AQDC = anthraquinone dicarboxylates, DMA = N,N-dimethylacetamide), with electron-accepting anthraquinone groups, generating two MOF guest charge transfer complexes: {Mn7(2,7-AQDC)6(2,6-AQDC)(DMA)6(TTF)5} and {Mn7(2,7-AQDC)6(2,6-AQDC)(DMA)4(H2O)2(TMPDA)7}. Using a mild impregnation procedure, single crystals of the target complexes were obtained via a crystal-to-crystal conversion, and the crystals were suitable for structural analysis. Single crystal X-ray analysis demonstrated the different arrangements of these intercalated donor molecules: some donor molecules interacted with the anthraquinone groups and formed infinite D-A-A-D stacks, some appeared beside the anthraquinone groups but only formed donor-acceptor pairs, and the remainder of the molecules simply filled the space. The charge transfer between the guests and the framework was spectroscopically confirmed, and the radical densities on the organic species were estimated using magnetic susceptibility measurements. Compared with a solid-state mixture of anthraquinone and donor molecules, the evenly distributed donor molecules in the micropores of the MOF resulted in a "solid solution" state and significantly promoted the degree of charge transfer between donors and acceptors. Such an encapsulation process may be adopted as a new strategy for post-modification of the electronic and magnetic properties of MOFs, as well as for generating new semiconducting charge-transfer complexes.

Factors affecting the polarity and magnitude of photoresponse of transient photodetectors.

The addition of an insulating layer (I) between one of the metal electrodes (M) and the photoactive semiconducting layer (S) in a standard organic MSM solar cell architecture changes the DC photocurrent response into a strong transient signal. Such a device can, in simple terms, be thought of as a charging voltage source (S) in contact with a charging capacitor (I). The magnitude of the photocurrent signal can be strongly enhanced through the intimate contact of the active layer with the insulating layer, if the various pre-polarizations within the device act synergically. In this study, the effect of the built-in potentials within the device on the polarity and magnitude of the photocurrent response is studied using the well-characterized bulk heterojunction blend system of poly(3-hexylthiophenone):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) as the semiconductor layer, and an ionic liquid as the insulating layer. This study shows that the polarity of the response is not simply determined by the energy level difference of the outer electrodes, but through a delicate interplay of all the energy levels in the device. Furthermore, these observations could be reproduced for devices with a solid-state insulator layer, where possible side-effects of the ionic liquid, such as swelling and doping, could be considered absent.

On-tip photodetection: a simple and universal platform for optoelectronic screening.

A novel platform for transient photodetector component screening has been developed whereby an optical fiber tip serves as the counter electrode when placed in a variety of dielectric media, connected to a photoresponsive working electrode. The soft processing conditions allow for ubiquitous photodetection for organic and biological systems.

Quasi-one-dimensional molecular magnets based on derivatives of (fluorobenzyl)pyridinium with the [M(mnt)2] monoanion (M = Ni, Pd or Pt; mnt2- = maleonitriledithiolate): syntheses, crystal structures and magnetic properties.

The syntheses, structural characterizations and magnetic behaviors of three new complexes, 1-(3',4',5'-trifluorobenzyl)pyridinium [M(mnt)2]- [M = Ni (1), Pd (2) or Pt (3)], are reported. These complexes are isomorphous and their prominent structural character is that the [M(mnt)2]- anions form columnar stacks, in which the dimerization was observed. Complexes 2 and 3 are diamagnetic, while 1 possesses an energy gap of 2474 K. For crystal 4, 1-(4'-fluorobenzyl)pyridinium [Ni(mnt)2] (its structure and magnetic susceptibility were briefly reported earlier), the magnetic behavior can be divided into two regimes, namely, weakly ferromagnetic coupling above 93 K and strongly antiferromagnetic coupling below 93 K. A transition occurs at 93 K which switches the magnetic exchange nature from ferromagnetic to antiferromagnetic. A sharp thermal abnormality with lambda-shape, associated with the transition, appears from its heat capacity measurement to indicate that the transition is first order. The temperature dependences of the superlattice diffractions revealed the existence of the pretransitional phenomena up to at least 140 K. The unusual magnetic behavior of 4, such as the origin of the ferromagnetic interaction in the high temperature phase and what causes the spin transition, are discussed further.

Structural phase transition driven by spin-lattice interaction in a quasi-one-dimensional spin system of [1-(4'-iodobenzyl)pyridinium][Ni(mnt)2].

Crystal structures and magnetic properties were determined for two novel compounds, [1-(4'-iodobenzyl)pyridinium][M(mnt)2] (mnt2- = maleonitriledithiolate; M = Ni (1) or Cu (2)). At room temperature, single crystals of 1 and 2 were isostructural, featuring the formation of segregated columnar structures with regular stacks of cations and anions. For crystal 1, a magnetic transition was observed at approximately 120 K; furthermore, its magnetic behavior was consistent with that of a regular Heisenberg antiferromagnetic (AFM) chain of S = 1/2 in the high-temperature phase (HT phase) and that of a spin-gap system in the low-temperature phase (LT phase). Such a phenomenon is similar to the spin-Peierls transition. However, the crystal structure of 1 in the LT phase at 100 K revealed that its structural transition is associated with the magnetic transition. Because crystal 2 (S = 0) did not exhibit a structural transition, the structural transition of 1 is driven by spin-lattice interaction.

Photoinduced phase transition in an organic radical crystal with room-temperature optical and magnetic bistability.

A phase control by photoirradiation is successfully achieved in a spin-Peierls system of the organic radical crystal, 1,3,5-trithia-2,4,6-triazapentalenyl (TTTA), which exhibits optical and magnetic bistability around room temperature with a large hysteresis loop. A nanosecond laser pulse is found to induce a transition from a diamagnetic low-temperature phase to a paramagnetic high-temperature phase both inside (296 K) and outside (11 K) the hysteresis loop. Comparison of the excitation energy dependence between transition efficiency and photoconductivity suggests that the photoinduced transition is driven by suppression of the spin-Peierls instability by the accumulation of photocarriers.

Single-molecule magnets: a new class of tetranuclear manganese magnets.

The preparation, X-ray structure, and detailed physical characterization are presented for a new type of single-molecule magnet [Mn4(O2CMe)2(pdmH)6](ClO4)2 (1). Complex 1.2MeCN.Et2O crystallizes in the triclinic space group P1, with cell dimensions at 130 K of a = 11.914(3) A, b = 15.347(4) A, c = 9.660(3) A, alpha = 104.58(1) degree, beta = 93.42(1) degree, gamma = 106.06(1) degree, and Z = 1. The cation lies on an inversion center and consists of a planar Mn4 rhombus that is mixed-valent, MnIII2MnII2. The pdmH- ligands (pdmH2 is pyridine-2,6-dimethanol) function as either bidentate or tridentate ligands. The bridging between Mn atoms is established by either a deprotonated oxygen atom of a pdmH- ligand or an acetate ligand. The solvated complex readily loses all acetonitrile and ether solvate molecules to give complex 1, which with time becomes hydrated to give 1.2.5H2O. Direct current and alternating current magnetic susceptibility data are given for 1 and 1.2.5H2O and indicate that the desolvated complex has a S = 8 ground state, whereas the hydrated 1.2.5H2O has a S = 9 ground state. Ferromagnetic interactions between MnIII-MnII and MnIII-MnIII pairs result in parallel spin alignments of the S = 5/2 MnII and S = 2 MnIII ions. High-frequency EPR spectra were run for complex 1.2.5H2O at frequencies of 218, 328, and 436 GHz in the 4.5-30 K range. A magnetic-field-oriented polycrystallite sample was employed. Fine structure is clearly seen in this parallel-field EPR spectrum. The transition fields were least-squares-fit to give g = 1.99, D = -0.451 K, and B4 degrees = 2.94 x 10(-5) K for the S = 9 ground state of 1.2.5H2O. A molecule with a large-spin ground state with D < 0 can function as a single-molecule magnet, as detected by techniques such as ac magnetic susceptibility. Out-of-phase ac signals (chi'' M) were seen for complexes 1 and 1.2.5H2O to show that these complexes are single-molecule magnets. A sample of 1 was studied by ac susceptibility in the 0.4-6.4 K range with the ac field oscillating at frequencies in the 1.1-1000 Hz range. A single peak in chi'' M vs temperature plots was seen for each frequency; the temperature of the chi'' M peak varies from 2.03 K at 995 Hz to 1.16 K at 1.1 Hz. Magnetization relaxation rates were evaluated in this way. An Arrhenius plot gave an activation energy of 17.3 K, which, as expected, is less than the 22.4 K value calculated for the thermodynamic barrier for magnetization direction reversal for an S = 8 complex with D = -0.35 K. The 1.2.5H2O complex with an S = 9 ground state has its chi'' M peaks at higher temperatures.

Room-Temperature Magnetic Bistability in Organic Radical Crystals.

A large first-order magnetic phase transition in an organic radical, 1,3,5-trithia-2,4,6-triazapentalenyl, is described. The transition occurs with a wide thermal hysteresis loop over the temperature range 230 to 305 kelvin. The high-temperature phase is paramagnetic, and its structure consists of a uniform one-dimensional stacking of the radical. The low-temperature phase is diamagnetic because of strong dimerization along the stacking direction. The results may have applications in thermal sensors, switching units, and information storage media based on organic radical crystals.