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High Pressure Coordination Chemistry: The Search for New Phenomena Alexander J. Blake School of Chemistry The University of Nottingham PACCON2014.

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Presentation on theme: "High Pressure Coordination Chemistry: The Search for New Phenomena Alexander J. Blake School of Chemistry The University of Nottingham PACCON2014."— Presentation transcript:

1 High Pressure Coordination Chemistry: The Search for New Phenomena Alexander J. Blake School of Chemistry The University of Nottingham PACCON2014

2  Introduction  Experimental  Initial results for [PdCl 2 ([9]aneS 3 )]  High pressure facilities  HP studies [MX 2 ([9]aneS 3 )] complexes [Pd([9]aneS 3 )(PPh 3 ) 2 ][PF 6 ] 2 [Pt([9]aneS 3 )(PPh 3 ) 2 ][PF 6 ] 2 Multi-phase [PdCl 2 ([9]aneS 2 O)]  Current and future work  Acknowledgements Outline of Talk

3 3 Pressure in the solar system 3 LocationPressure/bar Interplanetary space10 -9 Surface of Mars10 -2 Surface of the Earth1 Surface of Venus90 Marianas Trench1,100 Centre of Jupiter40,000,000 Centre of the sun150,000,000,000

4 4 Under our feet: pressure increases with depth 4 Depth /kmPressure/bar 3 (crust)1,000 400 (upper mantle ends)133,000 2900 (mantle/core boundary)1,300,000 6371 (centre of the earth)3,500,000

5 5 Pressure around us 5 SystemPressure/bar Car tyre2 Bicycle tyre8 Pressure washer100 Stiletto heel50-110 Rifle chamber4,000 Synthesis of diamonds55,000

6 6 Pressure in chemistry 6 ApplicationPressure/bar A hydrogenation reaction3 Ethene polymerisation10-40 Critical pressure for CO 2 73 Haber process200 KBr press for IR disks10,000

7 7 Very high pressures 7 Pressure /kbar Possible processes up to 100van der Waals space compressed 30-200coordination, packing changes 100melting point of ice = 400ºC 300-600deformation of covalent bonds 400organic solid-state reactions 1,000nearly all elements become metallic “very high”electrons move off atoms

8 8 High pressure crystallography from 1950’s onward initial interest from geophysics and astrophysics rocks, minerals, seismology, phase transitions planetary interiors from early 1990’s work on molecular compounds compressed liquids: acetone, phenol, alcohols solvates, pharmaceuticals, energetic materials

9 9 High pressure crystallography Very few metal-organic compounds reported, e.g. bis(dimethylglyoximato)platinum(II) O…O proton transfer spin-crossover in Fe(II) complexes resistivity in BEDT-TTF salts as a function of pressure pressure-dependence of structure in LiCp and KCp pressure-induced metal-to-insulator transitions in Pt(dmg) 2 metal-organic networks: (4-chloropyridinium) 2 [CoX 4 ]) some recent studies of copper complexes, MOFs, etc typically a few structures a year, but growing steadily J. P. Tidey, H. L. S. Wong, M. Schröder and A. J. Blake, Coord. Chem. Rev. 2014, submitted

10 Experimental – the Technology pressure = force/area 1 Nm -2 = 1 Pa = 10 -5 bar diamond anvil cell (~100 kbar) small sample compartment pressure-transmitting medium measure pressure by ruby fluorescence pressure = force/area 1 Nm -2 = 1 Pa = 10 -5 bar diamond anvil cell (~100 kbar) small sample compartment pressure-transmitting medium measure pressure by ruby fluorescence 10

11 Diamond Anvil Cell 5 cm fully assembled metal cell body Allen screws aperture (200 μm) support (goniometer head) fully assembled metal cell body Allen screws aperture (200 μm) support (goniometer head) Fits easily into the palm of a hand Fits a ‘standard’ X-ray diffractometer Fits easily into the palm of a hand Fits a ‘standard’ X-ray diffractometer 11

12 Experimental issues limited extent of data limited quality of data diamond reflection gasket sample reflection 12

13 Results for [PdCl 2 ([9]aneS 3 )] Pd1 Cl1 S4 C3 C2 S1 C9 C8 S7 Cl2 C6 C5 D.R. Allan, A.J. Blake, D. Huang, T.J. Prior, M. Schröder, Chem. Commun. 2006, 4081-4083 Square planar + 13

14 Response of [PdCl 2 ([9]aneS 3 )] Between ambient pressure and 76.8 kbar axial Pd … S 3.159(10)  2.771(13) Å intermolecular Pd … S 3.525(8)  3.006(10) Å intense colour change at 44 kbar ligand conformation [234] → [1233] unit cell volume contracts by 23% density increases from 2.105 to 2.732 g cm -3 Between ambient pressure and 76.8 kbar axial Pd … S 3.159(10)  2.771(13) Å intermolecular Pd … S 3.525(8)  3.006(10) Å intense colour change at 44 kbar ligand conformation [234] → [1233] unit cell volume contracts by 23% density increases from 2.105 to 2.732 g cm -3 14

15 [PdCl 2 ([9]aneS 3 )] - axial Pd … S1 distance contracts 3.009(5) Å 2.846(7) Å 42.5 kbar 46 kbar 15

16 [PdCl 2 ([9]aneS 3 )] 3.204(5) Å3.117(8) Å 42.5 kbar46 kbar - intermolecular Pd … S contracts - distorted octahedral coordination - chain polymer formed 16

17 [PdCl 2 ([9]aneS 3 )] 42.5 kbar46 kbar [234][1233] 17 - ligand changes conformation

18 [PdCl 2 ([9]aneS 3 )] 42.5 kbar46 kbar 18 - dramatic, reversible colour change

19 A short movie 19

20 Increasing pressure now … 20

21 21Diamond I19 Sample Environment Workshop 21-5-2013

22 22Diamond I19 Sample Environment Workshop 21-5-2013

23 23Diamond I19 Sample Environment Workshop 21-5-2013

24 24Diamond I19 Sample Environment Workshop 21-5-2013

25 25Diamond I19 Sample Environment Workshop 21-5-2013

26 26Diamond I19 Sample Environment Workshop 21-5-2013

27 27Diamond I19 Sample Environment Workshop 21-5-2013

28 28Diamond I19 Sample Environment Workshop 21-5-2013

29 29Diamond I19 Sample Environment Workshop 21-5-2013

30 Now decreasing pressure … 30

31 31Diamond I19 Sample Environment Workshop 21-5-2013

32 32Diamond I19 Sample Environment Workshop 21-5-2013

33 33Diamond I19 Sample Environment Workshop 21-5-2013

34 34Diamond I19 Sample Environment Workshop 21-5-2013

35 35Diamond I19 Sample Environment Workshop 21-5-2013

36 36Diamond I19 Sample Environment Workshop 21-5-2013

37 37Diamond I19 Sample Environment Workshop 21-5-2013

38 38Diamond I19 Sample Environment Workshop 21-5-2013

39 39Diamond I19 Sample Environment Workshop 21-5-2013

40 “Based on a true story …” The film you have just seen is based on real results, but does not represent an actual sequence of experiments. “No animals …” Unfortunately, several crystals were quite definitely harmed during the making of this film. “Based on a true story …” The film you have just seen is based on real results, but does not represent an actual sequence of experiments. “No animals …” Unfortunately, several crystals were quite definitely harmed during the making of this film. Disclaimers 40

41 High Pressure Crystallography Laboratory in Nottingham Oxford Diffraction (Agilent) SuperMovaII CCD diffractometer [Ancillary equipment for pressure measurement, etc.] 41

42 Diamond Light Source Oxfordshire, UK Very high intensity synchrotron X-ray source on Beamline I19 (EH1 and EH2) 2008–date Diamond Light Source Oxfordshire, UK Very high intensity synchrotron X-ray source on Beamline I19 (EH1 and EH2) 2008–date HP work at SRS and Diamond Synchrotron Radiation Source Daresbury Laboratory, Warrington, UK High intensity synchrotron X-ray source on Stations 9.8 and 16.2SMX 2005–2008 Synchrotron Radiation Source Daresbury Laboratory, Warrington, UK High intensity synchrotron X-ray source on Stations 9.8 and 16.2SMX 2005–2008

43 [MX 2 ([9]aneS 3 )] complexes studied at high pressure CompoundShort axial contact Chain polymer formed Ligand conformation changes Marked colour change Catenation induced [PdCl 2 ([9]aneS 3 )]  [PtCl 2 ([9]aneS 3 )]  [PdBr 2 ([9]aneS 3 )]  At 58 kbar PtBr 2 ([9]aneS 3 )]  At 58 kbar [PdI 2 ([9]aneS 3 )]  At 19 kbar [PtI 2 ([9]aneS 3 )]  At 19 kbar D. R. Allan, D. Bailey, N. Bird, A. J. Blake, N. R. Champness, D Huang, C. P. Keane, J. McMaster, T. J. Prior, J. P. Tidey & M. Schröder, Acta Crystallogr., Sect. B 2014, 70, 469−486. Daniel Bailey

44 Cation at 0.001 kbar Pressure-induced    stacking and molecular deformation in [Pd([9]aneS 3 )(PPh 3 ) 2 ][PF 6 ] 2  …  stacking Pyramidalisation at C11 at 65.5 kbar α = 149.3(8) ⁰ Pyramidalisation at C11 at 65.5 kbar α = 149.3(8) ⁰ Henry Wong H. L. S. Wong, D. R. Allan, N. R. Champness, J. McMaster, M. Schröder & A. J. Blake, Angew. Chem. 2013, 52, 5093–5095.

45 Current work: [Pt([9]aneS 3 )(PPh 3 ) 2 ][PF 6 ] 2 does not behave anything like the Pd analogue pressure does not induce  …  stacking no pyramidalisation at C11 under compression edge-to-face interactions are more important have preliminary results but need higher precision does not behave anything like the Pd analogue pressure does not induce  …  stacking no pyramidalisation at C11 under compression edge-to-face interactions are more important have preliminary results but need higher precision Jeremiah Tidey

46 Current work: [PdCl 2 ([9]aneS 2 O)] α-[PdCl 2 ([9]aneS 2 O)] - known phase: facially bound, endo macrocycle forms alternating sheets of Pd 2 dimers HP study complete γ-[PdCl 2 ([9]aneS 2 O)] - new phase: equatorially bound, exo macrocycle proto-chains via intermolecular Pd···O HP study complete 2.985(16) Å 3.768(4) Å 3.213(15) Å 3.39(2) Å 3.405(4) Å 3.4937(8) Å β-[PdCl 2 ([9]aneS 2 O)] - new phase: equatorially bound, exo macrocycle similar Pd 2 dimers as in the α form but different packing of these cutting transforms crystals to α form Jeremiah Tidey

47 Current work: [PdCl 2 ([9]aneS 2 O)] β-[PdCl 2 ([9]aneS 2 O)] is a possible “disappearing polymorph” see J. D. Dunitz & J. Bernstein, Acc. Chem. Res. 1995, 28, 193–200 formation of the β form may be kinetically favoured the γ polymorph may be more thermodynamically stable it may now be impossible to obtain the β form Jeremiah Tidey Multiple attempts over a year to regrow β-[PdCl 2 ([9]aneS 2 O)] different solvents and solvent mixtures different methods, techniques and variations all such efforts were uniformly unsuccessful Obtained stable crystals of β-[PtCl 2 ([9]aneS 2 O)] isomorphous with β-[PdCl 2 ([9]aneS 2 O)] used as a seed for epitaxial growth of β-[PdCl 2 ([9]aneS 2 O)] the disappearing polymorph has been recovered high pressure studies are underway on both complexes

48 Future work Central facilities Beamline I19 at Diamond Light Source – for any difficult cases – for structures near pressure limits Central facilities Beamline I19 at Diamond Light Source – for any difficult cases – for structures near pressure limits In-house high pressure laboratory all preliminary studies will be done here also most of the complete studies In-house high pressure laboratory all preliminary studies will be done here also most of the complete studies Main areas of investigation [M([9]aneS 3 ) 1-2 ] x+ [M([9]aneS 3 )PP] x+ [MX 2 ([9]aneS 2 O)] MOFs Main areas of investigation [M([9]aneS 3 ) 1-2 ] x+ [M([9]aneS 3 )PP] x+ [MX 2 ([9]aneS 2 O)] MOFs 48

49 49 Future work at Diamond Require the capabilities of EH2 Intensity, focussed beam, sample centring Require the capabilities of EH2 Intensity, focussed beam, sample centring High pressure studies on our new flexible MOFs Focus on MOFs with interesting properties High pressure studies on our new flexible MOFs Focus on MOFs with interesting properties Working at the limits of sample quality Need to optimise experimental conditions Develop the best experimental approaches Working at the limits of sample quality Need to optimise experimental conditions Develop the best experimental approaches

50 Acknowledgements Dr Dave Allan Professor Martin Schröder Professor Neil Champness Dr Jon McMaster Daniel Bailey Henry Wong Alice O’Connor Jeremiah Tidey 50 Dr Deguang Huang Dr Tim Prior (Daresbury) Tom McDonnell Conal Keane Nigel Bird Joe Cavan Dr John Warren (Daresbury) The Diamond I19 Team Professor Geoff Lawrance (Newcastle, AU)


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