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One-Pot Discovery of SFX-Linghai XIE 444
1. The discovery of one-pot protocol to
synthesize spiro[n]arenes
LingHai XIE (解令海)
Center for Molecular Systems and Organic Devices (CMSOD), Key Laboratory for Organic
Electronics and Information Displays & Institute of Advanced Materials (IAM), Jiangsu
National Synergistic Innovation Center for Advanced Materials (SICAM), Nanjing University
of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China.
E-mail: iamlhxie@njupt.edu.cn
Chicago, Illinois, USA July 17-19, 2017
2. Outline
• Background and Motivation
• An unexpected reaction for
SFX
• From SFX to other
spirofluorenes and spiroarenes
• Summary and Outlooks
• Acknowledgements
3. Spiro[n]arene as Subgroup of spiro
compounds
• Organic molecules can be simply regarded as carbon networks with capped hydrogens, which
range from small CH4 to large crystalline diamond. The chemical reactions that guide carbon
atoms to form an almost infinite set of ordered chemical structures give rise to the organic
complexity, which allows for molecular evolution of matter to produce life and intelligence on
earth.
• Spiro[n]arene is one of spiro compounds that are molecular networks of arenes via the cycle
linkage of covalent sp3 carbon.
Spiro[n]alkane Spiro[n]arene
Encyclopedia of Physical Organic Chemistry, 6 Volume Set. Zerong Wang (Editor), Uta Wille (Associate Editor), Eusebio Juaristi (Associate
Editor), ISBN: 978-1-118-47045-9, 4464 pages, February 2017. Volume 1. Part 1 Basic Terms and Theories 1, 3 Steric Strain in Molecular
Organics 161, Lei Yang, Linghai Xie, Ying Wei, Yuyu Liu, Murali Devi and Wei Huang.
4. Dye
sensitized
solar cell
OLEDs
OFETLasing
Perovskite
solar cells
SBF
Spirobifluorene (SBF) is one versatile building
block in organic electronics
• One impressive feature is the
obvious improvements of
thermal stability without
changing luminescence
• Key contribution to organic
electronics from Josef Salbeck
since 1997 (Synth. Met., 91(1997)
209.).
• SBFs have been extensively
applied in the field of OLEDs,
OPVs, transistors, lasers,
photodetectors, and other
devices.
Salbeck, J., Spiro compounds for organic optoelectronics. Chem. Rev. 2007, 107 (4), 1011-1065.
5. The detailed and key route of
spirofluroenes
• First synthesis by Clarkson RG and Gomberg M in 1930; this route have the advantage of substrate extension,
but there are drawback with expensive stuffs and laborious synthetic routes
• Our initial motivation is to obtain spirofluorenes via the green, eco-friendly as well as low cost route
Clarkson, R.G.; Gomberg, M. Spirans with four aromatic radicals on the spiro carbon atom. J. Am. Chem. Soc. 1930, 52, 2881–2891.
6. Another route is the one-pot protocol
of spirofluorenes
• The disadvantages of one-pot method: Limited
substrate extension and Limited reaction
mechanisms
Aromatic ketone (electron poor
or rich, nonplanar…)
Polycyclic aromatic phenols,
aromatic amines, thiophenols…
Uncommon carbon cationic pathway
Carbon anionic pathway
C-H activation
…
Adkins, H. J. Am. Chem. Soc. 1923, 45, 1030-1033; Korshak, V. V. et al. Russ Chem Bull, 1965, 14, 1256-1257
8. An occasional Reaction and Observation
• In order to synthesize the 4,4‘-(fluorene-9,9-diyl)diphenol derivatives, we make a general route of
double F-C reaction under the condition of Eaton's reagent according to a literature (Macromolecules
2002, 35, 9673-9677).
• However, the excessive methanesulfonic acid MeSO3H and the extension of reaction time can
provide SFXs in above 70% yield.
• Eaton's reagent[1] (7.7 wt% phosphorus pentoxide solution in methanesulfonic acid) is used as an alternative to polyphosphoric acid in
chemical synthesis to promote acylation reactions.
• Eaton, P. E.; Carlson, G. R.; Lee, J. T. (1973). “Phosphorus pentoxide-methanesulfonic acid. Convenient alternative to polyphosphoric
acid”. J. Org. Chem. 38 (23): 4071.
Xie, L. H.; Huang, W.; et al. Org. Lett. 2006, 8, 2787.
9. Pathway Analysis of One-pot Protocol to SFX
• A proof-of-concept models from SFX, starting point from one-pot protocol
to spirocyclic arenes
10. The plausible reaction mechanism of SFX
The role of excessive MeSO3H:
Acid catalyst in the Friedel-
Crafts process
Formation of the ether bond
Movement of the equilibrium to SFX
11. SYNFACT Highlight by Timothy M. Swager
Significance: In an attempt to make compound 1,
the authors fortuitously discovered a simple
one-pot procedure to prepare compound 2 with
any combination of H and Br at positions 2 and 7
of the fluorene ring system. Spiro compounds
like 2 are of interest because of their possible
utility in blue-light-emitting materials, as well as
other applications where the stability and
unique properties of the spiro-linkage offer
advantages. The authors performed solution-
and solid-state fluorescence studies on 3, a
model compound, to display its blue emission.
13. Korshak, V. V. et al. Russ Chem
Bull, 1965, 14, 1256-1257
Adkins, H. J. Am. Chem. Soc. 1923, 45, 1030-1033
Xie, L. H. et al. Org. Lett. 2006, 8, 2787-2790
The history and progress in one-pot
method of spiroarenes
14. SFXs with one-pot protocol that make it
possible in organic electronics
• By means of the concise and facile route to synthesize SFX, SFX have the potential
to applied various materials for organic devices
Xie, L. H.; Huang, W. et al. Org. Lett., 2006, 8, 2787. Xie-Huang, Current Organic Chemistry, 2010, 14, 2169-
2195. 林冬青等. 螺芴氧杂蒽(SFX)类有机半导体及其OLEDs. 科学通报, 2015, 60: 1–14
15. White TADF and device performance from
SFXSPO as universal host
CE (cd A-1)
50.5
CIE
40.6 19.1% (0.32, 0.43)
White Device PE (lm W-1) EQE
Maximum
J. Li, L. H. Xie, W. Huang, H. Xu et al. Adv. Mater., 2016, 28, 3122.
16. SFXSPO as universal host of TADFs
EQEmax 19.7%
DMAC-DPS 4CzCNPy
17.9%
4CzTPN 4CzPNPh 4CzTPNPh White
19.6% 22.5% 13.9% 19.1%
Device
J. Li, L. H. Xie, W. Huang, H. Xu et al. Adv. Mater., 2016, 28, 3122.
17. SFX-based perovskite solar cells with
enhanced stability
• Four spiro[fluorene-9,9′-xanthene] (SFX)-based hole transporting materials (HTMs)
functionalized with four-armed arylamine moieties located at different positions
are designed and synthesized.
Zhan XW et al., Mater. Chem. Front 2017, DOI:10.1039/c6qm00097eCollaboration with Prof Xiaowei Zhan
19. Licheng Sun and Anders Hagfeldt for X60
Devices with X60 as HTM showed high power conversion efficiencies
(PCEs) amounting to 7.30% in solid-state dye-sensitized solar cells
(ssDSCs) and 19.84% in perovskite solar cells (PSCs). The facile synthesis
of X60 from commercially available starting materials makes this HTM very
promising for large-scale industrial production in the future.
Anders Hagfeldt, Licheng Sun, Energy Environ. Sci., 2016, 9, 873-877
20. 在该文中（Energy Environ.
Sci., 2016, 9, 873--877），作
者通过“一锅法”构筑了基
于SFX的低成本的、易合成
的应用于太阳能电池的空穴
传输材料X60，并通过和经
典的基于SBF的Spiro-
OMeTAD空穴传输材料对比
，体现出X60更优异的性能
Bo Xu et al. Energy Environ. Sci., 2016, 9, 873--877
21. Synthesis cost estimation of
1 gram 4Br-SBF and 4Br-SFX
• According to the cost model that was described by
Pablo et al. and Osedach et al.
• The estimated synthesis cost of 4Br-SFX (1.12 $/g) is
30 times lower than that of the 4Br-SBF (33.89 $/g).
Anders Hagfeldt, Licheng Sun, Energy Environ. Sci., 2016, 9, 873-877
22. From SFX to other
spirofluorenes and spiroarenes
The above observation and impacts on organic electronics encourage us
universalizing the one-pot protocols of spirofluorenes
23. The universe formula of this reaction
• There are four parameters that could be changed; in order to
systemically examine the detailed conditions, we need do much work
that can not worthy to do. SFDBAO
Electron-rich substrates
Electron-withdrawing substrates
24. Progress in one-port protocol to
spirodiazafluorenes
• We have successfully overcome the difficulty of one-pot cascade reaction of SDAFs starting from
diazafluorenones and different phenols.
• The transformation to superelectrophiles of diazafluorenes provide carbon cationic
relay process, which novelly synthesizes SDAFXs in middle to high yields.
Lin D. Q.; Wei Y.; Xie, L. H.; Huang, W.; et al. Org. Lett. 2016, 18 (24), 6220–6223.
26. Expansion of the Substrate Scope
• SDAFX-derivatives using One-pot method with a highest yield of 92%
Lin D. Q.; Wei Y.; Xie, L. H.; Huang, W.; et al. Org. Lett. 2016, 18 (24), 6220–6223.
27. SDAFXs VS SFXs: intermediates
• Distinguished from SFX in terms of intermediates, the tertiary
alcohols rather than diaryl-diazafluorenes were produced.
Lin D. Q.; Wei Y.; Xie, L. H.; Huang, W.; et al. Org. Lett. 2016, 18 (24), 6220–6223.
28. Lin D. Q.; Wei Y.; Xie, L. H.; Huang, W.; et al. Org. Lett. 2016, 18 (24), 6220–6223.
SDAFXs VS SFXs: Plausible reaction pathways
• Differences between SDAFXs and SFX in one-pot pathways: 1) cationic relay; 2)
bond-linking sequence (C-C and C-O bonds)
29. Influence of SDAFXs
Apart from SFX, this work
has also been highlighted
by Timothy M. Swager and
You-chi Mason Wu L. in
Synfacts (2017, 13, 0256)
due to easier and more
efficient synthetic method of
spiro-diazafluorene
derivatives compared with
current synthetic strategy.
30. One of substrate is the electron-rich group
• To extend the scope of the method, we try to the synthesis of SDAFs using the substrate of diazafluorenes
• One-pot conception to construct sulfur-SFX. The difficulty is possible reason from the
higher activation on thiophenes, Friedel-Crafts polymerization to hyper branched polymers
proceeded while no corresponding spiroarene is obtained.
31. One-pot synthesis of sulfur-SFX
• When benzenes were introduced to block the reacted site
on thiophenes, we received sulfur-SFX in the high yield.
32. Beyond C-O bonding: Spiroacridine
• Polyphosphoric acid is the effective agent for SFDBA, and another visible light-
mediated reaction was found to give the unique building block of SFDBAO.
33. SFDBAO and its derivatives
Derivatives
Three bromo-reacted sites at SFDBAO can provide them with flexible fabrication.
a) Xie, L. H. et al. ACS NANO, 2012, 6, 5309–5319. b) Xie, L. H. et al. Adv. Mater. 2013, 25, 3664–3669.
35. Summary-I: Thistory and progress in one-pot method
of spiroarenes
Korshak, V. V. et al. Russ Chem Bull, 1965, 14, 1256-1257
Adkins, H. J. Am. Chem. Soc. 1923, 45, 1030-1033
Xie, L. H. et al. Org. Lett. 2006, 8, 2787-2790
Xie, L. H. et al. Org. Lett. 2016, 18, 6220−6223
36. Summary-II: From SBF to SFX, SDAFX, and SFDBAO
• Under the trend of eco-friendly green organic semiconductors for organic electronics, we
unexpected found a concise reaction to get access into spirofluorenes easily with the low-cost
advantages, especially for SFX-based Materials.
• We make attempt to universize the one-pot tandem protocols of SFX by changing the substrate of
phenols, fluorenones, and their conditions, spirodiazafluorenes were achieved by the mechanism
of supraelectrophiles with a cationic relay;
• Electron-rich and electron-withdraw substrates have been achieved to converse into orthogonal
shape spiro-configuration, together with the SDFBA via C-N bond+ two C-C bonds and another
unexpected SFDBAO was synthesized by visible light-mediated reactions.
37. Outlooks-I: To continuously complete the
one-pot method to spiroarenes
• Construction of fluorene-like spiroarenes using one-pot method
• There are some key substrates that are still failure to make cyclization and
how to design substrate to achieve the one –pot protocols of
spirobifluorenes?
• Construction of complicated building blocks in nano-size using
spiroarenes
38. Outlooks-II: Toward SFX-based Eco-friendly
Organic Semiconductors
• Green organic semiconductors (GOS) have the four-element features, including
biomass as stuffs, synthesis with the pot, atom and step economic (PASE) route,
eco-friendly fabrication processes in aqueous phase, and recyclable devices
High Energy-
consumption
Toxicity
Fossils
Multi-step
Eco-
friendly
inks
Recyclable
Devices
Biomass
PASE
route
with low
toxicity
Xie LH et. al., Chin. J. Chem. 2015, 33(8), 815–827.
39. Outlooks-III: To explore the engineering after science
• SFX via one-pot offer the input MEIC for engineering
SFX
Electrical
Engineering
Data
Engineering
Mechanical
Engineering
Molecular
Engineering
Chemical
Engineering
Era of
Consciousne
ss (EOC)
40. Members from Center for Molecular Systems and Organic Devices (CMSOD@IAM): Wei Huang (Academician); Prof. YI
Ming-Dong, QIAN Yan, SHI Nai-En, SONG Juan; Staff: LIU Yuyu, Wei Xue, Yongzhong Chang; ZHAO Jian-Feng, YIN
Cheng-Rong, LIN Jin-Yi, Ying Wei, FENG Qiangyou, BIAN Linyi, ZHAO Wei; PH D. SUN Mingli, LIN Zong-Qiong, LI
Wei-Jie, LI Wen, LING Haifeng, LIU Bin, OU Changjin, WANG Laiyuan, YU Yang…….
41. Financial Support
• This work was partially supported by National Natural Science Funds for
Excellent Young Scholar (21322402), National Natural Science Foundation
of China (U1301243, 21274064)
• The National Key Basic Research Program of China (973) (2015CB932200)
• The Program for New Century Excellent Talents in University (NCET-11-
0992), Doctoral Fund of Ministry of Education of China (20133223110007),
• Excellent science and technology innovation team of Jiangsu Higher
Education Institutions (2013) and Open Project from State Key Laboratory
of Supramolecular Structure and Materials at Jilin University
(sklssm2015022).
• Project was funded by the Priority Academic Program Development of
Jiangsu Higher Education Institutions
Eco Friendly Furniture & Green Design Ideas
reduce the cost
Spiro[fluorene-9,9′-xanthene]-based hole transporting materials for efficient perovskite solar cells with enhanced stability
Neil Robertson et al. J. Mater. Chem. A., 2016, 4, 4855.
A low-cost spiro[fluorene-9,9′-xanthene] (SFX) based organic hole transport material (HTM) termed X60 was designed and synthesized using a two-step synthetic route.
under 100 mW cm−2 AM1.5G solar illumination
SFX-based HTM for highly efficient DSSC and perovskite solar cells
To the best of our knowledge, this is the first example of an easily synthesized spiro-structured HTM that shows comparable performance with respect to the well-known HTM Spiro-OMeTAD in both ssDSCs and PSCs. Furthermore,
(10) Petrus, M. L.; Bein, T.; Dingemans, T. J.; Docampo, P. Journal of Materials Chemistry A 2015, 3, 12159.
(11) Osedach, T. P.; Andrew, T. L.; Bulovic, V. Energy & Environmental Science 2013, 6, 711.
The quotes (for bulk quantities when possible) have been collected from major chemical suppliers (Sigma-Aldrich, Alfa, TCI and Fischer) for all used chemicals.
Relay reactions induced by superelectrophiles serve as powerful tools to construct spirocyclic N-heterocycles-based building blocks. The first example that is the cationic relay protocol is reported to concisely synthesize spirodiazafluorenes (SDAFs) starting from diazafluorenones and phenols via one-pot method in the yields ranging from 7% to 92%. This cascade tandem reaction removes obstacle of the SDAFs to the application of organic/plastic electronics and biomedicine.
In addition, we found a interesting reaction with visible light-mediated reaction. a: SFDBA in sunlight before reaction; b: SFDBA in 365 nm Ultra-violet before reaction;
c: SFDBA in sunlight after reaction; d: SFDBA in 365 nm Ultra-violet after reaction
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![The discovery of one-pot protocol to
synthesize spiro[n]arenes
LingHai XIE (解令海)
Center for Molecular Systems and Organic Devices (CMSOD), Key Laboratory for Organic
Electronics and Information Displays & Institute of Advanced Materials (IAM), Jiangsu
National Synergistic Innovation Center for Advanced Materials (SICAM), Nanjing University
of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China.
E-mail: iamlhxie@njupt.edu.cn
Chicago, Illinois, USA July 17-19, 2017](https://image.slidesharecdn.com/sfxdiscovery-444-181225041219/85/One-Pot-Discovery-of-SFX-Linghai-XIE-444-1-320.jpg)
