MS MALDI-TOF analyses were run on Shimazu Axima-CFR spectrometer (mass range 20-150000Da); GCMS were run on Thermo Finnigan Polaris Q spectrometer using electron ionization (EI) mode (mass range 50-650Da). 

The high resolution mass measurements (pdf files marked "hrms") were performed on the Waters Xevo G2S instrument (ASAP-TOF-MS) or on Finnigan MAT 95XP (EI). 

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All spectra could be viewed via standard NMR software, such as MestReNova or TopSpin

1H and 13C NMR spectra were recorded on Bruker AVIII 400 apparatus at 400 MHz and 100 MHz, or Brucker AV500 at 500MHz and 125MHz. 

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A suitable orange block-shaped crystal of H1-PXZ-o(0.200×0.150×0.100) mm3 was selected and mounted on a MITIGEN holder in perfluoroether oil on a Rigaku 007HF diffractometer equipped with Varimax confocal mirrors and an AFC11 goniometer and HyPix 6000HE detector. The crystal was kept at T = 100(2) K during data collection. Using Olex2 (Dolomanov et al., 2009), the structure was solved with the ShelXT (Sheldrick, 2015) structure solution program, using the Intrinsic Phasing solution method. The model was refined with version 2014/7 of ShelXL (Sheldrick, 2015) using Least Squares minimisation.

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A suitable clear orange needle-shaped crystal of H1-PXZ-r (0.150×0.080×0.030) mm3 was selected and mounted on a MITIGEN holder in perfluoroether oil on a Rigaku FRE+ diffractometer equipped with HF Varimax confocal mirrors and an AFC12 goniometer and HyPix 6000HE detector. The crystal was kept at T = 100(2) K during data collection. Using Olex2 (Dolomanov et al., 2009), the structure was solved with the ShelXT (Sheldrick, 2015) structure solution program, using the Intrinsic Phasing solution method. The model was refined with version 2014/7 of ShelXL (Sheldrick, 2015) using Least Squares minimisation.

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A suitable yellow block-shaped crystal of H2PXZ (0.150×0.080×0.050) mm3 was selected and mounted on a MITIGEN holder in perfluoroether oil on a Rigaku 007HF diffractometer equipped with Varimax confocal mirrors and an AFC11 goniometer and HyPix 6000HE detector. The crystal was kept at T = 100(2) K during data collection. Using Olex2 (Dolomanov et al., 2009), the structure was solved with the ShelXT (Sheldrick, 2015) structure solution program, using the Intrinsic Phasing solution method. The model was refined with version 2014/7 of ShelXL (Sheldrick, 2015) using CGLS minimisation.

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All measurements were referenced to ferrocene (1-4).
Cyclic voltammetry measurements were performed using a CH Instruments 660A electrochemical workstation with iR compensation at a scan rate of 0.1 V s^(–1). The electrochemical cell comprised of glassy carbon, platinum wire and silver wire as working, counter and reference electrodes respectively. The experiments were conducted at room temperature in degassed (Ar) 0.1 M solutions of tetrabutylammonium tetrafluoroborate in dichloromethane with ca. 0.6 mM concentrations of studied compounds. 
All measurements were referenced against the half-wave potential (E1/2) of the Fc/Fc+ redox couple. The HOMO and LUMO levels were determined according to the following equations:
LUMO = – (Eox + 4.8) (eV)
HOMO = – (Ered + 4.8) (eV)

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Thermogravimetric analyses (TGA) were performed on the Perkin-Elmer Thermogravimetric Analyser TGA7 under a constant flow of Argon (20 mL/min). The temperature was raised at a rate of 10 °C min–1 from 40 °C to 500 °C.

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 Differential scanning calorimetry was carried on a TA Instruments Q1000 with a RC-90 refrigerated cooling unit attached. The test procedure was a standard Heat-Cool-Reheat, and the temperature range was from 25 °C to 300 °C at 10 °C min–1.

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All files numbers are corresponding to the figures in the paper.
The data can be processed using Origin or Excel software

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